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# The “𝑊=0” Pairing Mechanism from Repulsive Interactions in Symmetric 2𝑑 Models

## I Introduction

Most superconducting oxides have large unit cells containing four or more elements and CuO2 planes separated by intermediate layers which stabilize the lattice and act as a charge reservoir. A large amount of experimental and theoretical work has clarified that mobile holes on these planes are responsible for superconductivity. In the undoped solid the electrons are so strongly correlated that they cannot move freely as in a metal (antiferromagnetic Mott insulator). When holes are introduced into the plane by doping, the system becomes conducting and even superconducting provided the hole density is within the appropriate range. Increasing experimental evidence obtained in several cuprate superconductors has convincingly demonstrated that the pairing state of these materials has a non-trivial symmetry, ranging from $`s`$\- to $`d`$-wave. Moreover, the pairs exist above the critical temperature either in the form of superconducting fluctuations or preformed pairs. The latter aspect is apparent in the underdoped region in which a clear pseudogap essentially of the same magnitude as the superconducting gap is measured in ARPES, NMR, neutron scattering and specific heat measurement in metallic phase. All these signatures put strict constraints to any microscopic model of the cuprates. Any theory of the paired state must predict the correct symmetry and doping dependence of the binding energy of the pair, but the pairing mechanism must be doping-independent and robust enough to survive superconducting fluctuations well into the normal state, far from optimum doping.

The class of theories based on correlation mechanisms start from single or multiple bands Hubbard-like Hamiltonians containing nearest neighbors hopping matrix elements $`t`$ between Cu and O and O-O and large on-site Coulomb repulsive energies $`U`$ between holes of opposite spins which tends to reduce double occupancy of these sites. For $`U>>t`$, such Hamiltonians map into Heisenberg-like Hamiltonians for holes propagating through an antiferromagnetic background with an exchange interaction $`J`$ between neighboring spins. Perturbative approaches such as the t-J Model, by means of the Guzwiller projection force the holes to avoid on site interactions by letting $`U`$ to be very large (or infinite) so that eventually the pairing may be achieved through residual small attractive interactions. In this way the problem is circumvented formally, but not understood physically. Such models do not identify from the outset the physical mechanism capable to nullify the large repulsive Coulomb interactions among the paired holes. On one hand, the Guzwiller projection cuts a large part of the Hilbert space, and that would cost a catastrophic amount in kinetic energy, compared to the energy gain involved in the normal to superconductor transition, unless the repulsion is orders of magnitude larger than the hopping, which is not the case; on the other hand, the same idea could equally well be applied to a potato, i.e. it does not explain what is special in the CuO2 plane.

Due to the small size of the Cooper pairs, we believe that any serious proposal of a pairing mechanism should essentially be size-independent, i.e. it should work in the thermodynamic limit but it should be manifest in tiny systems as well. Exact calculations on finite models should bring to light interesting local aspects of the microscopic pairing mechanism, and be useful as tests for the analytic developments; pairing should be possible using a physically plausible range of parameter values.

In this review article, we illustrate the “$`W=0`$” pairing mechanism, which is specific of the square $`2d`$ structure of the CuO2 plane; instead of forcing the system by the Guzwiller projection we get the attraction by using the symmetry. The symmetry provides a physical mechanism capable of cutting down the on-site repulsion from the outset. We want to show that the holes avoid the on site interaction via a correlation mechanism which is effective for any $`U/t`$. We demonstrate this correlation effect, showing that its basic ingredient is a configuration mixing driven by the symmetry of the system which entails the presence of degenerate hole states at the Fermi level. Moreover, we provide evidence that the same configuration mixing, when applied to the many-body problem, also produces pairing between the holes and superconducting flux quantization when physical parameter values are used.

The work is divided into two main parts. In the first part, that is Section II, we review the pairing mechanism in small symmetric clusters. We begin by showing that by symmetry the Hubbard Hamiltonian admits two-hole singlet eigenstates that do not feel the on-site Hubbard repulsion, that we call $`W=0`$ pairs. First, we demonstrate that the prototype CuO4 cluster already contains the essential ingredients of the mechanism. Then we prove a general theorem on the allowed symmetries of $`W=0`$ pairs. From the theorem we extract a practical technique to build them explicitly for symmetric clusters and for the full plane. We will see that no $`W=0`$ pairs exist if the symmetry is too low. In Section II B we show that the peculiar properties of $`W=0`$ pairs cause a stabilization of the interacting system which leads to pairing. A careful analysis is made on the smallest “allowed” cluster, the CuO4; then, the investigation is extended to larger fully symmetric clusters. It is shown that pairing can be obtained in a physical parameter range any time the number of holes is “magic”. Section II C is devoted to the analytic interpretation of the results. It is shown that in second order perturbation theory the effective interaction between the holes of a $`W=0`$ pair comes out from the interference of positive and negative contributions, depending on the point symmetry of the electron-hole states exchanged, and that it may be attractive. Finally in Section II D we demonstrate the supercounducting flux quantization and conclude that $`W=0`$ pairs are the bare quasiparticles which become two-hole bound states when dressed by the interaction.

In the second part, that is Section III, we generalize the theory to the full plane. In Section III A, we review the band structure of the three-band Hubbard Model and fix some notations. In Section III B we show how $`W=0`$ pairs in the full plane arise at the Fermi level for any filling, and that their symmetry properties naturally lead to superconducting flux-quantisation. Section III C is devoted to the general canonical transformation leading to the effective Hamiltonian for pairs. The method is new and free from the limitations of perturbation theory; the relation of the present formalism to Cooper theory from one side and to the cluster results from the other is discussed. The final result of the analysis is an integral equation for pairs in the full plane, which is suitable for a numerical study. Therefore, in Section III D the integral equation is solved numerically. We first solve it in finite supercells and then take the asymptotic limit. Two kinds of bound states of different symmetries result, and the dependence of $`\mathrm{\Delta }`$ on the filling and other parameters is explored. Next, we study the Hubbard Model at and near half filling. Here the problem is that the non-interacting ground state at half filling is highly degenerate, while the canonical transformation needs a unique non-interacting ground state to work. Therefore, in Section III E we remove the degeneracy in first order perturbation theory by means of a suitable formalism, the local formalism, together with the help of a theorem by Lieb. The half filled ground state at weak coupling is explicitly written down. We show that it is the spin singlet projection of a peculiar determinantal state; the latter which exhibits the antiferromagnetic property: the translation by a lattice step is equivalent to a spin flip. In Section III F we use the $`4\times 4`$ square lattice as a test case. The half filled antiferromagnetic ground state is doped with two holes and an effective interaction between them is derived by means of the canonical transformation. The analytical results agree well with the numerical ones and this shows the predictive power of the approach. Finally, the main conclusions are summarized in Section IV.

## II Pairing in the Hubbard Model: Symmetric Clusters

Our starting point is the three-band Hubbard Model

$$H=K+W_{\mathrm{Hubbard}}+W_{\mathrm{off}\mathrm{site}}$$
(1)
where

$$K=\underset{ss^{},\sigma }{}t_{ss^{}}c_{s\sigma }^{}c_{s^{}\sigma }=t_{pd}\underset{ij,\sigma }{}(c_{j\sigma }^{}c_{i\sigma }+\mathrm{h}.c.)+t_{pp}\underset{jj^{},\sigma }{}(c_{j\sigma }^{}c_{j^{}\sigma }+\mathrm{h}.c.)+ϵ_d\underset{i,\sigma }{}\widehat{n}_{i\sigma }+ϵ_p\underset{j,\sigma }{}\widehat{n}_{j\sigma }$$
(2)
and

$$W_{\mathrm{Hubbard}}=U_d\underset{i}{}\widehat{n}_i\widehat{n}_i+U_p\underset{j}{}\widehat{n}_j\widehat{n}_j,W_{\mathrm{off}\mathrm{site}}=U_{pd}\underset{ij,\sigma \sigma ^{}}{}\widehat{n}_{i\sigma }\widehat{n}_{j\sigma ^{}}.$$
(3)
Here, $`c_j`$ ($`c_i`$) are fermionic operators that destroy holes at the Oxygen (Copper) ions labelled $`j`$ ($`i`$) and $`\widehat{n}=c^{}c`$ is the number operator. $`ij`$ refers to pairs of nearest neighbors $`i`$ (Copper) and $`j`$ (Oxygen) sites. The hopping terms corresponds to the hybridization between nearest neighbors Cu and O atoms, and are roughly proportional to the overlap between localized Wannier orbitals. $`U_d`$ and $`U_p`$ are positive constants that represent the repulsion between holes when they are at the same Copper ($`d`$) and Oxygen ($`p`$) orbitals, respectively. $`U_{pd}`$ has a similar meaning, i.e. it corresponds to the Coulombic repulsion when two holes occupy two adiacent Cu-O sites. The on site energies $`ϵ_p`$ and $`ϵ_d`$ represent the difference in energy between the occupied orbitals of Oxygen and Copper. In the strong coupling limit, and with one particle per unit cell, this model reduces to the spin Heisenberg Model with a superexchange antiferromagnetic coupling.

The Hamiltonian in Eq.(1) shows that for $`\mathrm{\Delta }_{pd}=ϵ_pϵ_d>0`$, the first hole added to the system will energetically prefer to occupy mostly the $`d`$-orbital of the Copper ions. This is indeed the observed situation in the undoped materials which have one hole per unit cell. When another hole is added to this unit cell, and working in the regime where $`U_d`$ is larger than $`\mathrm{\Delta }_{pd}`$, the new hole mainly occupy Oxygen orbitals. This is in agreement with Electron Energy Loss Spectroscopy experiments. From a band structure and by best fitting the results of up-to-date ab initio calculations one can roughly estimate the actual values of the parameters in the Hamiltonian of Eq.(1). Our preferred set***We are using a symmetric gauge; for instance, F. C. Zhang and T. M. Rice, Phys. Rev. B 37, 3759 (1988) use a different sign prescription for $`t_{pd}`$ and $`t_{pp}`$, which corresponds to changing the sign of some orbitals; using their convention, the orbital symmetry labels $`a_1`$ and $`b_1`$ get exchanged. is shown in Table I (in eV).

Several years ago, Hirsch and Scalapino introduced the quantity $`\mathrm{\Delta }(N)=E_0(N)+E_0(N2)2E_0(N1)`$, where $`E_0(N)`$ is the ground state energy of the system with $`N`$ holes. They showed by direct diagonalization of several clusters that $`\mathrm{\Delta }`$ can be negative with all positive Coulomb repulsion parameter. The $`\mathrm{\Delta }<0`$ behavior was taken as an indication that some kind of attraction was developing from repulsive interaction. From those calculations, it was apparent that negative $`\mathrm{\Delta }`$ arose from unphysically large Cu-O off-site interactions $`U_{pd}`$ of the order of 4-6 eV at least. Moreover the $`\mathrm{\Delta }<0`$ criterion has also been questioned because when one introduces the nuclear degrees of freedom, the sign of $`\mathrm{\Delta }`$ can be reversed. This can happen when the ground state with $`N1`$ holes is degenerate, and Jahn-Teller distorts, gaining energy by the distortion; the pairing then looks like an artifact due to the neglect of vibrations. Ultimately, the argument runs into trouble because it depends on a comparison of ground state energies with different hole numbers N.

In 1995, Cini and Balzarotti resumed the subject from a new standpoint which avoids the need for a large $`U_{pd}`$ and is free from the above criticisms. They started from the observation that highly-symmetric clusters possess 2-holes singlet eigenstates which do not feel the on-site repulsion $`W_{\mathrm{Hubbard}}`$, $`W=0`$ pairs. This property poses severe limitations on finite clusters that not only must possess the full $`C_{4v}`$ symmetry, but must be centered around a Cu site, see Figure 1.

Such $`W=0`$ eigenstates are generally excited states of the two-body system and arise when the two holes occupy degenerate states of $`E(x,y)`$ symmetry. The interesting situation arises when the hole population is such that the non interacting ground state would have two $`E`$ holes. Thus, any allowed cluster has its “magic” number of holes. The interacting ground state must be described in terms of a many-body configuration mixing, but the presence of the $`W=0`$ pair imparts to the many-body state a special character, as we shall show; the persistence of the “$`W=0`$” character in the interacting case is the main point that we want to make. The need for a partially filled shell restricts the hole numbers for small clusters, whereas of course any even number of holes works in the thermodynamic regime. In the infinite plane, $`W=0`$ pairs are easily obtained from the non-bonding band; a method for building them at any kinetic energy is discussed below.

Consider the process of filling the one-body levels of the noninteracting system according to the aufbau principle. Since the order of the one-body energy levels depends on the site energies and hopping integrals, for a given cluster the “last pair” is a $`W=0`$ pair in part of the parameter space. Therefore, $`W=0`$ pairs fix the cluster structure, occupation and the range of the parameters. These restrinctions are so stringent that these clusters with such properties had not been studied previously. In particular, the present discussion does not apply to the forbidden geometries, like those examined by Hirsch et al. and Balseiro et al.. The Cu4O4 geometry considered by Ogata and Shiba has the $`C_{4v}`$ symmetry of the lattice, but lacks the central Cu, and therefore it is forbidden (the pairs on degenerate levels feel the on-site repulsion, as one can see by performing the two-hole configuration interaction calculation). The dynamics of holes in Cu4O4 does not lead to pairing if the on-site repulsion on Oxygen is included.

### A $`W=0`$ Pairs

In this Section, we limit the discussion to on-site interactions ($`U_{pd}=0`$), while the effect of the off-site terms is deferred to Section II B.

#### 1 $`W=0`$ Pairs in the CuO4 Planar Cluster

For the sake of simplicity, let us first consider the CuO4 planar cluster of Figure 1 with 4 holes, one intrinsic and three due to doping. Site 1 is Cu, and the others are Oxygens. The single-hole energy level scheme vs. $`t_{pp}`$ is shown in Figure 2.

The levels are labelled according to the irreducible representations of the $`C_{4v}`$ symmetry Group whose character table is shown in Table II.

At $`t_{pp}=0.65`$ eV, the first two holes go into a bonding level of $`A_1`$ symmetry, and the next two go into a non-bonding level of $`E`$ symmetry, with orbitals transforming like the $`(x,y)`$ vector. Denoting the bonding state by $`a`$ and the degenerate non-bonding states by $`e_x`$ and $`e_y`$, one could build the degenerate singlet configurations $`|a_{}a_{}e_xe_x`$ and $`|a_{}a_{}e_ye_y`$ and the triplet components $`|a_{}a_{}e_xe_y`$ and $`|a_{}a_{}e_xe_y`$. Since parallel spin holes are not interacting in the model, in the Hartree-Fock (HF) approximation the triplet would have lower energy according to the Hund’s rule.

Yet, the singlet energy can be much improved by configuration interaction (CI). First, let us replace the $`(e_x,e_y)`$ pair by the $`(\alpha ,\beta )`$, where $`\alpha =(e_x+e_y)/\sqrt{2}`$ and $`\beta =(e_xe_y)/\sqrt{2}`$ are oriented in the O-O directions and are connected by a $`\pi /2`$ rotation. The singlet configurations then read $`|\mathrm{\Psi }_{\alpha \alpha }=|a_{}a_{}\alpha _{}\alpha _{}`$ and $`|\mathrm{\Psi }_{\beta \beta }=|a_{}a_{}\beta _{}\beta _{}`$, both with HF energy

$$\mathrm{\Psi }_{\alpha \alpha }|H|\mathrm{\Psi }_{\alpha \alpha }=\underset{\sigma }{}(K_{a\sigma }+K_{\alpha \sigma })+\underset{s}{}U_sn_{}(s)n_{}(s),$$
(4)
where $`s`$ denotes the generic site and $`U_s=U_d`$ if $`s`$ is a Cu site and $`U_s=U_p`$ otherwise. The first term on the right hand side contains the one-body contributions

$$K_{\phi \sigma }=\underset{s,s^{}}{}\phi _\sigma ^{}(s)t_{ss^{}}\phi _\sigma (s^{}),\phi (s)s|\phi ,\phi =a,\alpha $$
(5)
where $`t_{ss^{}}`$ is the hopping matrix element of the three-band Hubbard Model with diagonal entries $`t_{ss}=ϵ_d`$ ($`ϵ_p`$) if $`s`$ is a Cu (O) site, and $`n_\sigma (s)=|a_\sigma (s)|^2+|\alpha _\sigma (s)|^2n_a(s)+n_\alpha (s)`$. The configurations are mixed by $`\mathrm{\Psi }_{\alpha \alpha }|H|\mathrm{\Psi }_{\beta \beta }=_sU_sn_\alpha (s)n_\beta (s)`$. The lowest eigenvalue corresponding to the choice

$$|\mathrm{\Psi }^{()}=\frac{1}{\sqrt{2}}(|\mathrm{\Psi }_{\alpha \alpha }|\mathrm{\Psi }_{\beta \beta })$$
(6)
is

$$\epsilon =\mathrm{\Psi }_{\alpha \alpha }|H|\mathrm{\Psi }_{\alpha \alpha }\mathrm{\Psi }_{\alpha \alpha }|H|\mathrm{\Psi }_{\beta \beta }=\underset{\sigma }{}(K_{a\sigma }+K_{\alpha \sigma })+\underset{s}{}U_s[n_a^2(s)+2n_a(s)n_\alpha (s)]+W,$$
(7)
where $`W=_sU_sn_\alpha (s)[n_\alpha (s)n_\beta (s)]`$ represents the direct interaction between the non-bonding holes. At this point the issue is decided by the peculiar property of the system that $`n_\alpha (s)`$ and $`n_\beta (s)`$ are identical, despite the fact that the quantum states are distinct and orthogonal, and therefore the interaction between those holes is turned off exactly. We emphasized that the existence of degenerate states such that $`n_\alpha (s)=n_\beta (s)`$ is the only condition. This two-hole singlet eigenstate with vanishing on site repulsion is a $`W=0`$ pair. The above argument brings out the essential role of symmetry, and can be extended to clusters of arbitrary size. The singlet in Eq.(6) turns out to be $`{}_{}{}^{1}B_{2}^{}`$ which transforms as $`xy`$ and has a totally symmetric charge distribution.

Since $`W=0`$ for both $`{}_{}{}^{1}B_{2}^{}`$ and the triplet, two-body calculations cannot predict which is the ground state. In Section II B we shall show that pairing is indeed achieved in part of the parameter space and a non-degenerate singlet ground state prevails.

#### 2 $`W=0`$ Theorem

For any finite cluster having the full $`C_{4v}`$ symmetry and a Cu ion at the center, one can obtain $`W=0`$ pair eigenstates even if the above procedure is not directly extendible.

Here we want to point out a more powerful and elegant criterion to get all the $`W=0`$ pair eigenstates of a given system. As we shall see this criterion applies to Hubbard Models defined on an arbitrary graph $`\mathrm{\Lambda }`$. Let $`𝒢_0`$ be the the symmetry Group of the non-interacting Hubbard Hamiltonian $`K=_{xy\mathrm{\Lambda },\sigma }t_{xy}c_{x\sigma }^{}c_{y\sigma }`$. By definition, every one-body eigenstate of $`H_{\mathrm{Hubbard}}=K+W_{\mathrm{Hubbard}}`$, $`W_{\mathrm{Hubbard}}=_{x\mathrm{\Lambda }}U_x\widehat{n}_x\widehat{n}_x`$, can be classified as belonging to one of the irreducible representations (irreps) of $`𝒢_0`$. We may say that an irrep $`\eta `$ is represented in the one-body spectrum of $`H_{\mathrm{Hubbard}}`$ if at least one of the one-body levels belongs to $`\eta `$. Let $``$ be the set of the irreps of $`𝒢_0`$ which are represented in the one-body spectrum of $`H_{\mathrm{Hubbard}}`$. Let $`|\psi `$ be a two-body eigenstate of the non-interacting Hamiltonian with spin $`S^z=0`$ and $`P^{(\eta )}`$ the projection operator on the irrep $`\eta `$. We wish to prove the

$`W=0`$ Theorem. \- Any nonvanishing projection of $`|\psi `$ on an irrep not contained in $``$, is an eigenstate of $`H_{\mathrm{Hubbard}}`$ with no double occupancy. The singlet component of this state is a $`W=0`$ pair. Conversely, any pair belonging to an irrep represented in the spectrum must have non-vanishing $`W_{\mathrm{Hubbard}}`$ expectation value:

$$\eta W_{\mathrm{Hubbard}}P^{(\eta )}|\psi =0$$
(8)
Proof: Let us consider a two-body state of opposite spins belonging to the irrep $`\eta `$ of $`𝒢_0`$:

$$|\psi ^{(\eta )}=\underset{xy\mathrm{\Lambda }}{}\psi ^{(\eta )}(x,y)c_x^{}c_y^{}|0.$$
(9)
Then we have

$$\widehat{n}_x\widehat{n}_x|\psi ^{(\eta )}=\psi ^{(\eta )}(x,x)c_x^{}c_x^{}|0\psi ^{(\eta )}(x,x)|x,x.$$
(10)
We define $`P^{(\eta )}`$ as the projection operator on the irrep $`\eta `$. Since

$$P^{(\eta )}\underset{x\mathrm{\Lambda }}{}\psi ^{(\eta )}(x,x)|x,x=\underset{x\mathrm{\Lambda }}{}\psi ^{(\eta )}(x,x)|x,x$$
(11)
if $`P^{(\eta )}|x,x=0x\mathrm{\Lambda }`$ then $`\psi ^{(\eta )}(x,x)=0x\mathrm{\Lambda }`$. It is worth to note that this condition is satisfied if and only if $`P^{(\eta )}|x\sigma =0x\mathrm{\Lambda }`$ where $`|x\sigma =c_{x\sigma }^{}|0`$.

Now it is always possible to write $`|x\sigma `$ in the form $`|x\sigma =_\eta c^{(\eta )}(x)|\eta _\sigma `$ where $`|\eta _\sigma `$ is the one-body eigenstate of $`H_{\mathrm{Hubbard}}`$ with spin $`\sigma `$ belonging to the irrep $`\eta `$. Hence, if $`\eta ^{}`$, $`P^{(\eta ^{})}|x\sigma =0`$ and so $`P^{(\eta ^{})}|x,x=0`$. Therefore, if $`|\psi ^{(\eta )}`$ is a two-hole singlet eigenstate of the kinetic term and $`\eta `$, then it is also an eigenstate of $`W_{\mathrm{Hubbard}}`$ with vanishing eigenvalue, that means a $`W=0`$ pair.

There are cases when this theorem puts useful restrictions on the possible ground state symmetries; this happens when the ground state with $`N`$ holes corresponds to filled shells in the $`U0`$ limit and we wish to study the $`N+2`$ hole ground state. At least for small $`U`$ the two added holes will form a $`W=0`$ pair, since this minimizes the ground state energy. Let $`𝒢𝒢_0`$ be the symmetry Group of $`H_{\mathrm{Hubbard}}`$ and $`U_c(N)`$ the minimum crossover value of $`U`$, that is, the ground state with $`N`$ holes $`|\mathrm{\Phi }_U(N)`$ has well defined symmetry for $`0U<U_c(N)`$. Let $`|\mathrm{\Phi }_{U=0}(N)`$ be non-degenerate (e.g. closed shells case) and belong to the one-dimensional irrep $`\eta _0(N)𝒢_0`$. When we add the two extra holes, the new ground state for $`U=0`$ is a $`W=0`$ pair over $`|\mathrm{\Phi }_{U=0}(N)`$, and its symmetry is $`\eta _0(N)\eta _{W=0}`$, where $`\eta _{W=0}𝒢_0`$ is the symmetry of the added pair. Turning on the interaction $`\eta _0(N)\eta _{W=0}`$ breaks into the direct sum of irreps belonging to $`𝒢`$ and among them there must be the symmetry of $`|\mathrm{\Phi }_U(N+2)`$ if $`0U<U_c(N+2)`$. This remarkable restriction is posed by Group Theory alone: which of the symmetries that remain allowed is actually realised in the ground state depends on the dynamics.

The complete characterization of the symmetry of $`W=0`$ pairs requires the knowledge of $`𝒢_0`$. A partial use of the theorem is possible if one does not know $`𝒢_0`$ but knows a Subgroup $`𝒢_0^<`$. It is then still granted that any pair belonging to an irrep of $`𝒢_0^<`$ not represented in the spectrum has the $`W=0`$ property. On the other hand, accidental degeneracies occur with a Subgroup of $`𝒢_0`$, and by mixing degenerate pairs belonging to irreps represented in the spectrum one can find $`W=0`$ pairs also there.

The theorem tells us that the bigger is $`𝒢_0`$, the larger is the number of $`W=0`$ pairs. Indeed, for a given graph, the number of one-body eigenvectors is fixed, while the number and the dimension of the $`𝒢_0`$ irreps grow with the order of the group. Therefore, also the number of irreps not represented in $``$ grows, and this means more $`W=0`$ pairs. At the same time, a big “non-interacting” symmetry Group $`𝒢_0`$ grants large level degeneracies. As we have seen, this fact allows the existence of $`W=0`$ pairs formed by degenerate orbitals. In the next Section we show that an anomalously low effective repulsion takes place in the interacting system when such levels are on the Fermi surface and that in a certain region of the parameters space this leads to pairing.

Finally we observe that the $`W=0`$ theorem predicts $`W=0`$ pairs of $`A_2`$ and/or $`B_2`$ symmetry in the CuO4 cluster, as one can see by inspection of Figure 2. This is consistent with the above results where the symmetry of the $`W=0`$ pair in Eq.(6) was estimated to be $`B_2`$. Further, when $`t_{pp}=0`$, the non-bonding levels $`e`$ and $`b_1`$ in Figure 2 become degenerate and a new $`W=0`$ pair of $`A_1`$ symmetry is obtained. At a first sight, this fact seems to contradict the $`W=0`$ theorem, but it is not so. As we have observed before, unexpected symmetries arise if one use a Subgroup of $`𝒢_0`$. For $`t_{pp}=0`$, the extra degeneracy cannot be explained in terms of the $`C_{4v}`$ Group, whose irreps have dimensions 2 at most. It is not hard to realize that for $`t_{pp}=0`$ any permutation of the four Oxygen sites is actually a symmetry and therefore the symmetry Group is enlarged to $`\mathrm{\Pi }_4`$ (the group of permutations of four objects) which admits irreps of dimension three. Then, labelling the one-body levels with the irrep of $`\mathrm{\Pi }_4`$, one readly realize that irreps not contained in the spectrum give $`W=0`$ pairs, according to the $`W=0`$ theorem, and that among them there is one containing the $`A_1`$ irrep of $`C_{4v}`$.

### B CI and Exact Solutions for Symmetric Clusters

In the present Section, we wish to show how $`\mathrm{\Delta }<0`$ may be induced by symmetry through degeneracy.

#### 1 $`\mathrm{\Delta }<0`$ in the CuO4

Let us first consider the CuO4 cluster with four holes in the non-interacting limit: according to the aufbau the first two holes go into a bonding level of $`A_1`$ symmetry and the next two into a non-bonding level of $`E`$ symmetry. Group Theory predicts that the interactions resolves the sixfold-degenerate ground state $`EE`$ into $`{}_{}{}^{3}A_{2}^{}`$, $`{}_{}{}^{1}A_{1}^{}`$, $`{}_{}{}^{1}B_{1}^{}`$ and $`{}_{}{}^{1}B_{2}^{}`$. The two- body calculations say that $`{}_{}{}^{1}B_{2}^{}`$ and the triplet are lowest, since $`W=0`$ for both. The ground state will turn out to be singlet, while Hund’s rule would have predicted $`{}_{}{}^{3}A_{2}^{}`$; we shall see why and how low spin prevails.

In Table III we report the ground state energies $`E_0(N)`$ of the CuO4 cluster with $`N`$ holes, $`N=1`$ to 4, and the effective repulsion energy $`\mathrm{\Delta }(4)=E_0(4)2E_0(3)+E_0(2)`$.

While $`W`$ gives the direct interaction between the two holes in the CI calculation, $`\mathrm{\Delta }(4)`$ contains indirect interaction as well. The HF results correspond to a spontaneously broken symmetry of the 4-hole singlet and fail to reproduce the quantum effect we are discussing. Accordingly, the effective on-site repulsion is $`\mathrm{\Delta }(4)=1.46`$ eV, which is quite a large repulsive barrier to overcome before pairing can be attained. In the CI calculation it is assumed the form (6) for the wave function and optimized the energy with respect to the orbitals. This does lead to a small negative estimate for $`\mathrm{\Delta }(4)`$. The exact diagonalization with the same parameters yields a positive but tiny $`\mathrm{\Delta }(4)`$ with a $`{}_{}{}^{1}B_{2}^{}`$ ground state (the symmetry of the $`W=0`$ pair), while the first excited state is a $`{}_{}{}^{3}A_{2}^{}`$ triplet lying $`D=18`$ meV above it. This suggests the interpretation that $`W=0`$ two-hole eigenstates are bare quasiparticles and their attractive screened interaction produces the pairingWe note that the experimental evidence on the symmetry of the pairs is still conflicting, and different techniques tend to give different results. Angular resolved photoemission data favour $`d`$ pairs with an order parameter of $`{}_{}{}^{1}B_{1}^{}(x^2y^2)`$ simmetry. The $`W=0`$ pair of symmetry $`{}_{}{}^{1}B_{2}^{}(xy)`$ is consistent with these findings, since its total-symmetric charge density has nodes at 45 degrees from the Cu-O axis. Phases are less significant, and we can switch irreps by a gauge transformation. In the full plane the present approach also predicts $`W=0`$ pairs of different symmetries, and the symmetry of the most bound pairs depends on the filling. It is fair to say that this problem is far from being settled. . Although the CI calculation gives a negative $`\mathrm{\Delta }(4)`$ value, the exact calculation yelds a tiny positive one. However, if $`t_{pp}`$ is increased, $`\mathrm{\Delta }(4)`$ does become negative, which shows that the correlation effects may lead to pairing (see Table IV).

Even if the estimation of the singlet-triplet gap depends on the parameters, it is consistent with the 45 meV excitation observed in High Resolution Electron Energy Loss spectra and the 41 meV resonance found in Polarized Neutron Scattering experiments on superconducting YBa2Cu3O7.

The maximum binding energy occurs at $`t_{pp}=0`$, when all the non-bonding orbitals are degenerate and the configuration mixing is thereby enhanced. On the other hand, at positive $`t_{pp}`$’s, $`\mathrm{\Delta }(4)`$ becomes large and positive, because the $`b_1`$ non-bonding level is pushed below the degenerate one, and the mechanism is hampered (at $`t_{pp}=+0.65`$, $`\mathrm{\Delta }(4)=0.53`$ eV).

Next, we discuss the dependence of $`\mathrm{\Delta }(4)`$ on the other parameters. If we decrease $`ϵ_p`$, $`\mathrm{\Delta }(4)`$ decreases because this makes the system more polarizable. The $`ϵ_p`$ dependence when all the other parameter are kept fixed and $`U_{pd}=0`$ is almost linear down to $`ϵ_p=0`$. By contrast, the dependence of $`\mathrm{\Delta }(4)`$ on the Cu-O hopping parameter $`t_{pd}`$ is complex. For small $`t_{pd}`$, $`\mathrm{\Delta }(4)`$ is large and positive, then falls to zero at $`t_{pd}0.7`$ eV. Negative $`\mathrm{\Delta }(4)`$ values are obtained for $`t_{pd}1.4`$ eV. Finally let us consider the effects of a non-vanishing $`U_{pd}`$. According to Ref. positive $`U_{pd}`$ values do not spoil the mechanism, and tend to be synergic with it. Indeed, values of $`U_{pd}>0.6`$ eV give negative $`\mathrm{\Delta }(4)`$ values even for $`t_{pp}=0.65`$ eV (in the range 0.2-1.2 eV considered in Ref. $`\mathrm{\Delta }(4)`$ is a monotonically decreasing function of $`U_{pd}`$).

As we have seen, symmetry plays a key role in the analytical calculations; the numerical results on the CuO4 cluster further demonstrates the fact that any lowering of the symmetry is reflected by a corresponding increase of $`\mathrm{\Delta }(4)`$. This implies that the CI mechanism is working thanks to the $`C_{4v}`$ symmetry, and it is cut off whenever the symmetry is lowered.

#### 2 $`\mathrm{\Delta }<0`$ in Symmetric Clusters

The total hole concentration which corresponds experimentally to the superconducting state is $`\rho _h0.4`$ per atom. In the CuO4 cluster we need four holes to operate the CI mechanism, because we need holes in degenerate states. Therefore $`\rho _h`$ is too large by a factor of two, and the $`W=0`$ pair involves nonbonding states, which are far from the Fermi level in the bulk. It is important to realize that these undesirable features are peculiar of the prototype CuO4 cluster, and already disappear in Cu5O4, the next larger cluster of the same symmetry, see Figure 1. In fact, four holes are still sufficient to reach degenerate states, as shown in Figure 3 ($`a`$), but $`\rho _h0.44`$ is much closer to the experimental value.

The degenerate states are bonding, in contrast with the CuO4 case, and the holes now spend a large fraction of their time on Cu sites. The effective interaction $`\mathrm{\Delta }(4)`$ for Cu5O4 and the spin triplet separation $`D`$ vs. $`t_{pp}`$ is shown in Figure 3 ($`b`$). $`\mathrm{\Delta }(4)`$ is negative in a wide parameters range by a correlation mechanism that does not need off-site $`U_{pd}`$ to operate. To visualize the physical effects of the effective attraction, one can compare the ground-state charge distribution for the non-interacting and interacting holes. When $`\mathrm{\Delta }(4)<0`$, the charge distribution shrinks; besides, the holes tend to accumulate more on the Oxygens where their mutual repulsion is mitigated by the CI mechanism. The opposite takes place in the “unpaired” region where the charge of the two least bound holes piles up preferentially on the external Cu sites. The size of the problem with four holes is 1296; it reduces to 81 on projecting to the $`{}_{}{}^{1}B_{2}^{}`$ symmetry of the ground state, while the symmetry of the first excited state is a $`{}_{}{}^{3}A_{2}^{}`$ triplet. As in the CuO4 cluster the maximum binding energy occurs at $`t_{pp}=0`$ and takes the value $`\mathrm{\Delta }(4)=15.7`$ meV; thus the binding energy $`|\mathrm{\Delta }(4)|`$ is about half the CuO4 value. For larger clusters the computational effort is more demanding (44.100 configurations for the Cu5O16). For $`t_{pp}=0`$, and $`U_{pd}=0`$, it was found that $`\mathrm{\Delta }(4)=7.5`$ meV in the Cu5O16 planar cluster (with $`U_{pd}=1`$ eV, $`\mathrm{\Delta }(4)=7.6`$ meV). The calculated trend of $`\mathrm{\Delta }(4)`$ with the number of atoms $`|\mathrm{\Lambda }|`$ is shown in Figure 4 ($`a`$). The decline of $`\rho _h`$ with increasing number of atoms is slow enough to allow a significant contribution to the binding energy for cluster sizes that correspond to the actual size ($`\xi 1020`$ $`\stackrel{}{A}`$) of the superconducting pair.

As shown in Figure 3 ($`a`$), there are two degenerate levels available to test the $`W=0`$ pairing mechanism; moreover electron pairs and hole pairs are related by an approximate charge conjugation symmetry and we can perform the test by filling the levels from bottom to top and the other way. The Cu5O4 Hamiltonian was diagonalized and the ground state energy was obtained as a function of the number $`N`$ of holes. Eventually, we find electron pairing with a binding energy $`\mathrm{\Delta }(N)`$ of a few tenth of meV in the physical parameter space.

Let us consider the three-band Hubbard Hamiltonian of Eq.(1). By a canonical transformation from holes to electrons, $`c_{s\sigma }c_{s\sigma }^{}`$, we get for $`U_{pd}=0`$

$$H=\underset{s}{}(2ϵ_s+U_s)\underset{s\sigma }{}(ϵ_s+U_s)c_{s\sigma }^{}c_{s\sigma }\underset{s,s^{}\sigma }{}t_{ss^{}}c_{s\sigma }^{}c_{s^{}\sigma }+\underset{s}{}U_s\widehat{n}_s\widehat{n}_s.$$
(12)
Thus, in the electron representation the signs of the site and hopping integrals are reversed. With respect to the hole case, the sequence of single-electron energy levels of the Cu5O4 cluster is such that bonding and antibonding states are interchanged. In the hole representation the antibonding state of $`e`$ symmetry contains two holes when 12 holes are present in the cluster. Therefore $`N_h`$=4, 12 are magic numbers (to avoid confusion we will denote by $`N_h`$ ($`N_e`$) the number of holes (electrons)). In the electron representation $`W=0`$ electron pairs are obtained for $`N_e=4`$, 12. Letting $`E_0^{(e)}(N_e)`$ be the ground state energy of the cluster with $`N_e`$ electrons, the effective interaction between the two electrons in the pair is measured by

$$\mathrm{\Delta }_e(N_e)=E_0^{(e)}(N_e)+E_0^{(e)}(N_e2)2E_0^{(e)}(N_e1).$$
(13)
Since the dimensionality of the one-body basis is 18

$$\mathrm{\Delta }_e(4)=E_0^{(e)}(4)+E_0^{(e)}(2)2E_0^{(e)}(3)=E_0^{(h)}(14)+E_0^{(h)}(16)2E_0^{(h)}(15)=\mathrm{\Delta }_h(16)$$
(14)
where $`E_0^{(h)}(N_h)`$ is the ground state energy of the cluster with $`N_h`$ holes. Similarly one finds $`\mathrm{\Delta }_e(12)=\mathrm{\Delta }_h(8)`$.

We recall that we speak of electron pairs when two added electrons partially occupy a degenerate state and of hole pairs when the same situation is reached by adding two holes; however the final situation is exactly the same. One readily verifies that in a canonical transformation from holes to electrons the two-hole state becomes a two electron state of the same form. Therefore the two-body $`W=0`$ state is invariant under charge conjugation, and if holes are paired, electrons are also paired. In order to avoid switching all the time between the two equivalent pictures, below we discuss everything in terms of holes.

In the symmetric Cu5O4 cluster we previously found that the exact diagonalization of the Hamiltonian matrix with four holes in a wide range of negative $`t_{pp}`$ values for the $`{}_{}{}^{1}B_{2}^{}`$ singlet gives a negative $`\mathrm{\Delta }(4)`$. Therefore one expects that $`\mathrm{\Delta }(N_h)`$ is small or negative for $`N_h=`$ 4, 8, 12 and 16 and large and positive for any other $`N_h`$.

The $`t_{pp}`$ dependence of $`\mathrm{\Delta }(N_h)`$ computed using an enhanced Lanczos diagonalization routine  is shown in Figure 4 ($`b`$) and ($`c`$) for $`\mathrm{\Delta }(4)`$ and $`\mathrm{\Delta }(16)`$ and for $`\mathrm{\Delta }(10)`$ and $`\mathrm{\Delta }(14)`$, respectively. In Table V we summarize the results for $`\mathrm{\Delta }(N_h)`$ when the model parameters are fixed according to the Table I but $`t_{pp}=0`$ and for a wide range of $`N_h`$. One sees that for $`N_h=`$ 4, 8, 12 and 16 $`\mathrm{\Delta }`$ is much smaller in absolute value than for other fillings, as predicted. This confirms that $`W=0`$ pairs are involved.

It is apparent that a considerable degree of symmetry under e-h exchange exists in the cluster and that the pairing interaction is not restricted to a single value of doping. The electron-hole symmetry is not exact, because the one-electron energy level spectrum of Figure 3 ($`a`$) is not invariant when up is exchanged with down and left with right ($`t_{pp}t_{pp}`$ and $`EE`$); however one could have predicted the negative $`\mathrm{\Delta }`$ and its magnitude by the approximate symmetry. In real systems electron superconductivity has been first reported in the Nd2CuO4 doped with Ce with a maximum $`T_c`$=24 K for optimal doping concentration $`\delta `$=0.15, similarly to more common hole superconductors. Nd2-δCeδCuO4 is an example of high-$`T_c`$ cuprate in which charged carriers are electrons.

To summarize, in this Section we have shown that a correlation effect (namely, the CI mechanism) leads to negative $`\mathrm{\Delta }`$ values by means of the exact removal of the direct Coulomb interaction between pairs of degenerate hole states. The CI mechanism is a consequence of the symmetry and electronic structure of the CuO2 plane, and do not depend on the size of the cluster. The concept of $`W=0`$ pairs is useful already at a qualitative level to make predictions about the behaviour of interacting many-body systems, and this is quite remarkable and unusual. Any large deviation from the full symmetry restores the normal on-site repulsion The binding energy $`\mathrm{\Delta }`$ is of the correct order of magnitude (10 meV) for the set of parameters which corresponds to the best current estimates for the actual system. In the next Section we will definitively remove the ambiguity concerning the physical meaning of $`\mathrm{\Delta }`$. We will show that in fully simmetric clusters, as the ones studied above, negative $`\mathrm{\Delta }`$ corresponds to pairing.

### C The Physical Meaning: Effective Interaction

In this Section we show that in the Hubbard Model the negative-$`\mathrm{\Delta }`$ behaviour due to the “$`W=0`$” mechanism has the physical meaning of hole pairing, due to an effective attraction between the holes of the $`W=0`$ pair. The fact that pairing occurs can be estabilished by the following argument. Consider a system $`\mathrm{\Sigma }`$ consisting of a couple of identical clusters (say, CuO4) that we denote $`\mathrm{\Sigma }_a`$ and $`\mathrm{\Sigma }_b`$. Let $`\mathrm{\Sigma }_a`$ and $`\mathrm{\Sigma }_b`$ be placed one on top of the other and suppose the two systems are linked by a interplane hopping integral $`\tau <<\mathrm{\Delta }(4)`$ as shown in Figure 5.

Such an arrangement is chosen arbitrarily for the sake of definiteness, but the important thing is that the two clusters are linked in such a way that the $`C_{4v}`$ symmetry is not disturbed and the magnitude of $`\tau `$ is such that its influence on the ground state energy is negligible compared to the other energies of the system. We may then write the full Hamiltonian as $`H=H_{\mathrm{\Sigma }_a}+H_{\mathrm{\Sigma }_b}+H_\tau `$ and regard the weak link term $`H_\tau `$ as a perturbation. In zeroth order, $`H`$ can be diagonalized simultaneously with the occupation numbers $`N_{\mathrm{\Sigma }_a}`$ and $`N_{\mathrm{\Sigma }_b}`$ of the two clusters. The interesting situation arises when the number of holes in $`\mathrm{\Sigma }`$ is $`N=N_{\mathrm{\Sigma }_a}+N_{\mathrm{\Sigma }_b}=6`$. The nature of the ground state depends on the parameters. The “normal” state is obtained if $`\mathrm{\Delta }(4)>0`$; the unperturbed ground state is $`|\mathrm{\Phi }_{\mathrm{normal}}=|N_{\mathrm{\Sigma }_a}=3|N_{\mathrm{\Sigma }_b}=3`$, that is, the product of the individual ground state of two $`{}_{}{}^{2}E`$ independent clusters containing three holes each. The unperturbed ground state energy is $`2E_0(3)`$.

On the other hand, if $`\mathrm{\Delta }(4)<0`$, that means $`E_0(4)+E_0(2)<2E_0(3)`$, the zeroth order ground state is

$$|\mathrm{\Phi }_{\mathrm{paired}}=\frac{|N_{\mathrm{\Sigma }_a}=4|N_{\mathrm{\Sigma }_b}=2\pm |N_{\mathrm{\Sigma }_a}=2|N_{\mathrm{\Sigma }_b}=4}{\sqrt{2}}$$
(15)
and the system prefers to disproportionate. It is clear that $`\mathrm{\Delta }(4)`$ is just the energy needed to break the pair. The $`\pm `$ sign arises because the system has a bonding and an antibonding level; to lowest order, the two levels are separated by an energy of the order of $`\tau ^2/|\mathrm{\Delta }|`$. If the system is prepared with a pair of holes in one of the planes, it evolves in such a way that the pair will jump back and forth from $`\mathrm{\Sigma }_a`$ to $`\mathrm{\Sigma }_b`$ with that frequencyWe remark that interplane oscillations (Josephson plasma mode) had been observed in La2-δSrδCuO4, see Ref... This is clear evidence for pairing; if many systems like $`\mathrm{\Sigma }`$ are connected by weak links in a similar way, pairs will propagate§§§Due to the mixing of degenerate states, the ground states of $`\mathrm{\Sigma }`$ belonging to positive and negative $`\mathrm{\Delta }(4)`$ also belong to different symmetries. Indeed $`|\mathrm{\Phi }_{\mathrm{paired}}`$ is nondegenerate, since $`|N_{\mathrm{\Sigma }_a}=4`$ is $`{}_{}{}^{1}B_{2}^{}`$ while $`|N_{\mathrm{\Sigma }_b}=2`$ is $`{}_{}{}^{1}A_{1}^{}`$. On the other hand, $`{}_{}{}^{2}E`$ is fourfold degenerate and $`|\mathrm{\Phi }_{\mathrm{normal}}`$ has degeneracy 8 in the $`S^z=0`$ subspace..

Next, we want to show that in the Hubbard Model the pairing is due to an effective attraction between the holes of the $`W=0`$ pair. This point is more suble; one could argue that $`\mathrm{\Delta }<0`$ depends on a comparison of ground state energies of systems with different hole numbers N, and hence it is not obvious that it is a property of any of them. Moreover, the definition of $`\mathrm{\Delta }`$ in terms of systems with different numbers of particles leads to a further difficulty. When one introduces the vibrational degrees of freedom, the state with a sigle hole in the degenerate level can gain energy by a Jahn-Teller distortion. The sign of $`\mathrm{\Delta }`$ can even be reversed. The pairing then looks like an artifact due to the neglect of the vibrations. Therefore we want an alternative definition of $`\mathrm{\Delta }`$ which is equivalent to the previous one at weak coupling but depends exclusively on the properties of the Hubbard Model in the presence of the pair.This argument clarifies the nature of the pairing in the Hubbard Model, which is due to an effective attraction leading to a bound state. Including vibrational degrees of freedom in the description of a cluster or a plane, what the system would do with more or less holes than it actually has is unimportant if we can define the pairing by means of an effective interaction. Much more complex modeling would of course be necessary to study coupled subsystems like those of Figure 5 in the presence of vibrations.  We first show how to define the effective interaction in clusters, where we may take advantage from the exact diagnalizations. In all the allowed clusters up to 21 atoms, the lowest one-hole level belongs to $`A_1`$ symmetry, and the next $`e`$ level yields the $`W=0`$ pair. In the previous Section we noted that the interactions produce a non-degenerate $`{}_{}{}^{1}B_{2}^{}`$ 4-hole ground state with $`\mathrm{\Delta }<0`$. Below, it is shown that in the case of dressed $`W=0`$ singlet pairs, $`\mathrm{\Delta }<0`$ arises from an effective pairing interaction which is attractive; the same interaction is repulsive for triplet pairs. The argument rests on a comparison of the perturbation series for $`\mathrm{\Delta }`$ and for the two-hole amplitude; for the dressed $`W=0`$ pair the two-hole amplitude actually involves $`\mathrm{\Delta }`$ and yields its dynamical interpretation.

#### 1 Diagrams for $`\mathrm{\Delta }`$

The perturbation series for $`\mathrm{\Delta }`$ in powers of $`U`$ is obtained by the well-known diagrammatic expansion of the ground state energy $`E_0`$ of a many body system. This is based on the theorem

$$E_0=E_0^{(0)}+i\underset{t\mathrm{}(1i\eta )}{lim}\frac{d}{dt}\mathrm{ln}\stackrel{~}{R}(t)$$
(16)
where $`E_0^{(0)}`$ is the non interacting ground state energy, $`\eta =+0`$;

$$\stackrel{~}{R}(t)=\mathrm{\Phi }_0|U(t)|\mathrm{\Phi }_0,$$
(17)
$`|\mathrm{\Phi }_0`$ is the non interacting ground state, and $`U(t)`$ is the time evolution operator in the interaction representation. One then expands the correlation function $`\stackrel{~}{R}(t)`$ using the linked cluster theorem, that simplifies the expansion, but the diagrams that violate the Pauli principle and/or the number of particles must be retained. The diagrammatic rules are readily applied to the $`N=2`$ case, when $`|\mathrm{\Phi }_0`$ is a non degenerate single-determinant state. For $`N=3`$ and $`N=4`$, the non interacting ground state is degenerate, while the derivation of Eq.(16) assumes that the interactions do not modify the symmetry of the ground state; therefore we take $`|\mathrm{\Phi }_0`$ as the $`x`$ component of the $`{}_{}{}^{2}E`$ irreducible representation for $`N=3`$ and $`{}_{}{}^{1}B_{2}^{}`$ for $`N=4;`$ we know from direct diagonalization that these symmetries are correct for the whole series of clusters. For $`N=4`$ the $`{}_{}{}^{1}B_{2}^{}`$ component of the non interacting ground state reads

$$|\mathrm{\Phi }_0=\frac{|e_xe_y+|e_ye_x}{\sqrt{2}}$$
(18)
where in terms of orbitals $`|e_xe_y`$ is the state $`|a_{}a_{}e_xe_y_{}`$. Since this cannot be written as a single determinant, some care is necessary in the diagrammatic expansion; the correlation function is

$$\stackrel{~}{R}(t)=e_xe_y|U(t)|e_xe_y+e_ye_x|U(t)|e_xe_y.$$
(19)
Applying the linked cluster theorem, the first term leads to the standard diagrams, while the second is anomalous, in the sense that it vanishes in the non interacting limit. Thus, one finds all the diagrams contributing to the expansion for $`U(t)`$ averaged over $`|a_{}a_{}e_xe_y_{}`$, plus the anomalous or spin-flip diagrams that have entering $`e_x`$ and $`e_y`$ and outgoing $`e_y`$ and $`e_x`$ lines, see Figure 6 (A).

Let $`W(k,l,m,n)`$ $`=k_{}l_{}|W_{\mathrm{Hubbard}}|m_{}n_{}`$; the anomalous diagram can be obtained from the normal one, which is proportional to $`W(a,b,e_x,e_x)^2`$, simply by letting $`W(a,b,e_x,e_x)W(a,b,e_y,e_y)`$ in the upper interaction line. A sign change follows, in agreement with the standard diagrammatic rules. In summary, one starts the expansion as if the ground state were the single determinant $`|a_{}a_{}e_xe_y_{}`$; the diagrams that involve propagating $`e_x`$ and $`e_y`$ lines get corrections, which are obtained by exchanging $`e_x`$ and $`e_y`$ in the upper interaction line where the $`e_x`$ or $`e_y`$ lines end; the loose lines should then be joined, and the diagram so obtained carries a minus sign because of the change in the number of loops. It is convenient to denote the hole orbitals by $`b`$ for the $`b_1`$’s and $`a`$ ($`a^{}`$) for the occupied (empty) orbitals $`a_1`$. After some algebra, one obtains the second-order approximation to $`\mathrm{\Delta }(4)`$

$$\mathrm{\Delta }^{(2)}(4)=2\left[\underset{b}{}\frac{W(a,b,e_x,e_x)^2}{(ϵ_bϵ_a)}\underset{a^{}}{}\frac{W(a,a^{},e_x,e_x)^2}{(ϵ_a^{}ϵ_a)}\right],$$
(20)
where $`ϵ_a`$ is the one-hole energy of the $`a`$ orbital and so on; the sums run over all empty states of the appropriate symmetries ($`a_1`$ and $`b_1`$), while no contributions arise from the empty $`e`$ orbitals since the relevant $`W_{\mathrm{Hubbard}}`$ matrix elements vanish. Eq.(20) holds for any symmetric cluster up to 21 atoms. The sign of $`\mathrm{\Delta }`$ is seen to depend on the relative weight of the virtual transitions to states of different point symmetry, and ultimately on the parameters in the Hamiltonian.

#### 2 Diagrams for the Two-Hole Amplitude

Let $`G_2`$ denote the two-hole amplitude for holes of opposite spin in the degenerate $`(e_x,e_y)`$ orbitals. Singlet and triplet arise from the space spanned by the non-interacting states $`|e_xe_y`$ and $`|e_ye_x`$, which are connected by $`C_{4v}`$ operators. In the Nambu formalism, $`G_2`$ is a matrix

$$G_2(\omega )=\left(\begin{array}{cc}A& A_{sf}\\ A_{sf}& A\end{array}\right);$$
(21)
here $`A`$ is a normal propagator, while $`A_{sf}`$ involves a spin-flip and vanishes in the non-interacting limit. When interactions are included, the first order contribution to the scattering amplitude vanishes because the product of $`e_x`$ and $`e_y`$ orbitals vanishes on all sites. Therefore, the spin-flip process, $`A_{sf}`$, shown in Figure 6 (B), is the lowest-order $`e_xe_y`$ scattering, and produces the effective interaction to second-order. The system makes virtual transition to 4-body (3 holes and 1 electron) states.

Evaluating $`A_{sf}`$ according to the standard rules, one finds that near $`\omega =2ϵ_e`$, $`A_{sf}\frac{i\mathrm{\Delta }^{(2)}(4)}{(\omega 2ϵ_e)^2}`$ +less singular terms; moreover, to second order, $`A=\frac{i}{\omega 2ϵ_e}`$. We know from symmetry that $`G_2(\omega )`$ has singlet and triplet eigenvectors $`\frac{1}{\sqrt{2}}(1,\pm 1)`$; for the singlet and triplet we get

$$A+A_{sf}=\frac{i}{\omega \eta _s},AA_{sf}=\frac{i}{\omega \eta _t},$$
(22)
where $`\eta _{s,t}`$ are the new eigenvalues. Therefore, for the singlet the expansion is

$$\frac{1}{\omega \eta _s}\frac{1}{\omega 2ϵ_e}+\frac{\mathrm{\Delta }^{(2)}(4)}{(\omega 2ϵ_e)^2}\frac{1}{\omega 2ϵ_e\mathrm{\Delta }^{(2)}(4)},$$
(23)
that is $`\eta _s=2ϵ_e+\mathrm{\Delta }^{(2)}(4)`$; the triplet receives the opposite correction, and the $`{}_{}{}^{1}B_{2}^{}^3A_2`$ separation is $`D=2|\mathrm{\Delta }(4)|`$. Negative $`\mathrm{\Delta }(4)`$ means that the spin-flip interaction is attractive for $`{}_{}{}^{1}B_{2}^{}`$ which is pushed down by $`|\mathrm{\Delta }(4)|`$ and becomes the ground state, while the triplet is pushed up by the same amount. In this way, $`\mathrm{\Delta }(4)`$ can be redefined without any reference to the ground state of clusters with a different numbers of holes, and we are free from the objections based on the Jahn-Teller distorsion of odd-$`N`$ clusters.

Since $`U_p`$ and $`U_d`$ are not small compared to the Cu-O hopping term $`t_{pd}`$, the second-order is generally a poor approximation; interestingly, $`W=0`$ pairs are an exception, because the large interactions are dynamically small. The first-order term vanishes, and the second order is of the order of tens of meV. Comparison with exact numerical diagonalization results shows that the second-order approximation for $`D`$ and $`\mathrm{\Delta }(4)`$ is already rewarding. In Figure 4 ($`a`$) it is shown how $`D`$ and $`\mathrm{\Delta }(4)`$ scale with the cluster size; they are indeed very closely proportional, although their ratio is somewhat larger than 2. Thus, the comparison with $`D`$ is useful to show that $`\mathrm{\Delta }(4)`$ really measures a property of the 4-hole state, and that the two $`E`$ symmetry holes actually experience attraction.

### D Superconducting Flux Quantization

We test the paired state by exposing the system to a vector potential $`𝐀(𝐫)`$ according to the Peierls prescription,

$$t_{ss^{}}t_{ss^{}}\mathrm{exp}[\frac{2\pi i}{\varphi _0}\underset{s}{\overset{s^{}}{}}𝐀𝑑𝐫],$$
(24)
where $`\varphi _0=2\pi /e`$ is the flux quantum, and looking for superconducting correlations. In a macroscopic experiment, one makes a sample with a large hole, and inserts a magnetic field; the ground state energy $`E_0(\varphi )`$ is trivially a periodic function of $`\varphi /\varphi _0`$, where $`\varphi `$ is the flux in the tube, and $`\varphi =0`$ is an extremumA flux $`\varphi =\varphi _0`$ can be gauged away, and any physical property, for example the ground state energy, is a periodic functions of $`\varphi `$ with period $`\varphi _0`$.. Superconductors quantize the flux by allowing integer and half-integer multiples of $`\varphi _0`$, because the quasiparticles that screen the vector potential carry charge $`2e`$. A flux $`\varphi _0/2`$ corresponds to a superconducting ground state with pairs having different symmetry than those prevailing at $`\varphi =0`$, and the system is stable; arbitrary $`\varphi `$ values are not allowed because they cost large amounts of (free) energy.

Canright and Girvin have shown that cluster calculations can be used to obtain qualitative insight on the occurrence of superconductivity, by looking for a tendency to flux quantization. The signature is present when $`\varphi =0`$ is a minimum of $`E_0(\varphi )`$ and the only other minimum of comparable depth occurs at $`\varphi /\varphi _0=\frac{1}{2}`$; the barriers separating the minima are small in a small system but one expects them to increase with size, leaving the flux quantized in units of $`\varphi _0/2`$. Canright and Girvin used a square lattice of rectangular geometry and periodic boundary conditions along one of the axes; to demonstrate the effect, they assumed an attractive on-site interaction and observed superconducting flux quantization for even hole numbers and strong enough attraction. In the present problem, with a repulsive Hubbard Model, the mechanism of attraction is driven by the $`C_{4v}`$ symmetry, and cannot operate with such an unsymmetric geometry. The flux must be inserted in such a way that the system is not distorted. We must insert the flux tube inside allowed clusters, but since no closed path encircling the central Cu is available for the holes, there is no response to a central flux tube.

Cini and Balzarotti used an external device providing a closed path around the flux tube. The device, however, cannot be chosen arbitrarily, because the cluster must remain allowed and the singlet pair must remain one with $`W=0`$. To fulfill this condition, Cini and Balzarotti introduce an infinitesimal hopping $`t_{dd}`$ between the external Cu’s (see the inset of Figure 7) and study the linear response to this perturbation\**\**\**Due to the smallness of the system under study, the hopping parameter $`t_{dd}`$ that contribute a closed path around the central Cu must be kept very small to prevent the magnetic perturbation from growing large and destroying the structure of the ground state multiplet. Numerically, the computations were performed with $`t_{dd}=\pm 0.01`$ eV.. This geometry is a compromise, because the magnetic field penetrates our small cluster; however, it lends itself to an extension to the full plane, such that only the 4 central plaquettes feel a magnetic field, and the rest of the plane only experiences a vector potential (see Section III). The relevant response function $`R`$ is

$$R\left(\varphi \right)=\frac{E_0(\varphi )E_0(0)}{t_{dd}}$$
(25)
and depends on the test flux $`\varphi `$ (in units of $`\varphi _0`$). The results for Cu5O4 and Cu5O16 with 4 holes are shown in Fig.7; the same trend is obtained for all clusters. The minimum at $`\varphi _0/2`$ is the microscopic precursor of the superconducting flux quantization; by looking at $`\mathrm{\Delta }(4)`$ and analyzing the numerical ground state wave functions at $`\varphi _0/2`$ one finds that it corresponds to pairs of $`{}_{}{}^{1}A_{1}^{}`$ symmetry which are bound, since the minimum at half flux quantum corresponds again to a $`\mathrm{\Delta }(4)<0`$ situation. Thus the point symmetry of the wavefunction changes from $`{}_{}{}^{1}B_{2}^{}`$($`x^2y^2`$) at $`\varphi =0`$ to $`{}_{}{}^{1}A_{1}^{}`$($`x^2+y^2`$) at $`\varphi =\varphi _0`$/2.

This finding is a much clearer signature of superconducting flux quantisation than the generally accepted presence of the two minima, because it implies that the superconductor remains a superconductor after swallowing up the half flux quantum. Therefore, in order to determine the flux dependence of the effective interaction, one can compute $`\mathrm{\Delta }(N,\varphi )`$. It was found that when $`\mathrm{\Delta }(N,0)<0`$, then $`\mathrm{\Delta }(N,\varphi _0/2)`$ is also negative.

Quite different patterns in which the flux quantization is absent are obtained for two and three holes. Also, it is clear that it is $`W_{\mathrm{Hubbard}}`$ that forces the paired holes to screen the vector potential like a charge $`2e`$; actually, the non interacting case is quite different. If the input data are modified in such a way that $`\mathrm{\Delta }`$ becomes positive by severe distortion of the symmetry, the characteristic central minimum is lost altogether.

By looking at Fig.7 we realize that with increasing the flux $`\varphi `$, the $`{}_{}{}^{1}B_{2}^{}`$ component of the ground state is quickly destabilized by the vector potential, while the $`{}_{}{}^{1}A_{1}^{}`$ component decreases in energy and eventually becomes energetically favored in presence of the trapped flux. A similar change of symmetry occurs in conventional superconductors where the Cooper wavefunction has $`s`$-wave symmetry in absence of magnetic flux.

These findings are required by general symmetry principles. In the absence of $`t_{dd}`$, the full invariance Group of the cluster is $`\mathrm{\Pi }_4`$ and, as we have seen above, the interacting ground state is degenerate, with $`{}_{}{}^{1}A_{1}^{}`$ and $`{}_{}{}^{1}B_{2}^{}`$ components. A nonzero $`t_{dd}`$ at $`\varphi =0`$ reduces the symmetry to the $`C_{4v}`$ Subgroup; it turned out numerically that with a positive $`t_{dd}`$ ($`t_{dd}=0.01`$ eV in our calculations) the expectation value of the magnetic perturbation is negative on $`{}_{}{}^{1}B_{2}^{}`$ and positive on $`{}_{}{}^{1}A_{1}^{}`$; therefore the ground state is $`{}_{}{}^{1}B_{2}^{}`$ at $`t_{dd}>0`$ but changes symmetry if the sign of $`t_{dd}`$ is reversed. Upon switching the vector potential $`𝐀`$, the Cu-Cu hopping is complex and chiral, so the symmetry is lowered again from $`C_{4v}`$ to its Subgroup $`𝐙_4`$, which contains only the rotations. Since $`𝐙_4`$ is Abelian, there are no degeneracies for a generic $`\varphi `$, so there are no $`W=0`$ pairs and therefore repulsion prevails. With increasing the flux from 0, the ground state energy increases to a maximum. Then it decreases because, at $`\varphi =\varphi _0/2`$, the Cu-Cu hopping of Eq.(24) becomes $`t_{dd}`$, which is real; then the full $`C_{4v}`$ symmetry is restored, resurrecting the $`W=0`$ pairs. The recovery of $`C_{4v}`$ at $`\varphi =\varphi _0/2`$ enables us to assign the eigenvectors to the irreps, as noted above. The change of symmetry of the pair is also readily understood: the perturbation caused by $`t_{dd}>0`$ at $`\varphi =0`$ becomes the opposite at half fluxon, so the $`{}_{}{}^{1}A_{1}^{}`$ state is lowest now. The signature of superconducting pairing is not only the existence of a well defined second minimum at half flux quantum, but also the fact that it corresponds to a pairing ($`\mathrm{\Delta }<0`$ ) situation, like at $`\varphi =0`$. It is gratifying that the present model allows for $`W=0`$ pairs of both symmetries, because this is the only way the superconducting flux quantization works.

Finally, it is worth to note that the Hubbard large $`U`$ system is stabilized by the intrinsic charge fluctuation. Since the mechanism is robust (first order) it is conceivable that these low lying pairing states can survive in the vortex core of the underdoped phase.

## III Pairing in the Hubbard Model: General Theory

The CuO2 plane and the clusters that possess the same $`C_{4v}`$ symmetry around a Cu ion have 2-hole eigenstates of the kinetic energy with vanishing on-site repulsion ($`W=0`$ pairs). Cluster calculations by exact diagonalisation show that these are the quasiparticles that lead to a paired ground state, and have superconducting flux-quantisation properties. In this Section, we extend the theory to the full plane, and show that the $`W=0`$ quasiparticles are again the natural explanation of superconducting flux quantisation. Moreover, by a novel canonical tranformation approach, we calculate the effective interaction $`W_{\mathrm{eff}}`$ between two holes added to the ground state of the repulsive Hubbard Model. The method is a particularly efficient way to perform the configuration interaction calculation. It is based on the symmetry, and dramatically displays the mechanism of pairing in the CuO2 plane. We show that the full configuration interaction calculation can be performed recursively. At each step, one decouples a class of virtual excitations while renormalising the matrix elements of the kinetic term $`K`$ and of the Hubbard repulsion $`W_{\mathrm{Hubbard}}`$. At the end, one obtains an exact, analytical canonical transformation producing an effective Hamiltonian for the dressed pair. In order to get actual numbers, however, we had to neglect the renormalizations in the final formula; this approximation is fully justified at weak coupling. Thus, a closed-form analytic expression including the effects of all virtual transitions to 4-body intermediate states (exchange of an electron-hole pair) is derived. The effective interaction is the result of a partial cancellation of positive and negative contributions, so it is not necessarily attractive in all cases; the general signature of $`W=0`$ pairs is that the absolute value of the interaction is much smaller than in the other cases. Since $`W=0`$ pairs emerge from symmetry alone, they remain $`W=0`$ for any coupling strength and are an adequate starting point for a realistic theory. This is the reason why weak coupling expansions often provide good approximations at intermediate coupling, as observed by several authors.

The main scheme is ready to include other interactions which are not considered in the Hubbard Model but may be important. We find that the effective interaction is attractive and leads to a Cooper-like instability of the Fermi liquid, while it is repulsive for triplet pairs. From $`W_{\mathrm{eff}}`$, an integral equation for the pair eigenfunction can be derived; the binding energy $`|\mathrm{\Delta }|`$ of the pairs is in the range of tens of meV, which is not comparable to any of the $`U`$ and $`t`$ input parameters. The reason is that the interaction, which vanishes identically for the bare $`W=0`$ pairs, remains dynamically small for the dressed quasiparticles. This suggests that a weak coupling theory may be useful to study the pairing force, despite the fact that $`U`$ is not small compared to $`t`$.

### A Band Structure

Let us consider the three-band Hubbard Hamiltonian. The kinetic term is

$$K=\underset{s,s^{}}{}t_{ss^{}}c_{s\sigma }^{}c_{s^{}\sigma }+\underset{s}{}ϵ_sc_{s\sigma }^{}c_{s\sigma }$$
(26)
where $`t_{ss^{}}=t_{pd}`$ if $`s`$ and $`s^{}`$ represent a Copper site and a nearest neighbor Oxygen site, or viceversa, and zero otherwise, while $`ϵ_s=ϵ_p`$ if $`s`$ is an Oxygen site and zero otherwise. It is convenient to identify each unit cell by its cartesian coordinates $`𝐫=(i_x,i_y),i_x,i_y=1,\mathrm{},N_\mathrm{\Lambda }`$ ($`N_\mathrm{\Lambda }^2=|\mathrm{\Lambda }|/3`$ being the total number of unit cell) in such a way that $`𝐫`$, $`𝐫+𝐚`$ and $`𝐫+𝐛`$ are the positions of the Cu and of the two Oxygens, respectively. The one-body eigenstates of $`K`$ are

$$Kc_{𝐤\sigma }^{(\nu )^{}}|0=ϵ_𝐤^{(\nu )}c_{𝐤\sigma }^{(\nu )^{}}|0,𝐤=(k_x,k_y)=\frac{2\pi }{N_\mathrm{\Lambda }}(i_x,i_y),i_x,i_y=1,\mathrm{},N_\mathrm{\Lambda },$$
(27)
where $`\nu `$ is a band index and periodic boundary conditions are chosen. According to Bloch’s theorem they can be written as

$$c_{𝐤\sigma }^{(\nu )^{}}=\underset{s}{}c_{s\sigma }^{}\psi ^{(\nu )}(𝐤,s),\psi ^{(\nu )}(𝐤,s)=e^{i𝐤𝐫}\phi ^{(\nu )}(𝐤,s)$$
(28)
where $`\phi ^{(\nu )}`$ has the lattice periodicity and $`𝐫`$ is the position of the cell in which the site $`s`$ lies. The non-bonding band is characterized by $`\phi ^{(nb)}(𝐤,0)=0`$; one then finds

$$\phi ^{(nb)}(𝐤,𝐚)=\frac{1}{N_\mathrm{\Lambda }}\frac{\mathrm{cos}\left[\frac{k_x}{2}\right]}{\sqrt{\left(\mathrm{cos}^2\left[\frac{k_x}{2}\right]+\mathrm{cos}^2\left[\frac{k_y}{2}\right]\right)}},\phi ^{(nb)}(𝐤,𝐛)=\frac{1}{N_\mathrm{\Lambda }}\frac{\mathrm{cos}\left[\frac{k_y}{2}\right]}{\sqrt{\left(\mathrm{cos}^2\left[\frac{k_x}{2}\right]+\mathrm{cos}^2\left[\frac{k_y}{2}\right]\right)}}.$$
(29)
For the other bands, one obtains the eigenvalue equation

$$ϵ_𝐤^{(\pm )}=\frac{ϵ_p\pm \tau }{2},\tau =\sqrt{ϵ_p^2+16t_{pd}^2\left[\mathrm{cos}^2\left[\frac{k_x}{2}\right]+\mathrm{cos}^2\left[\frac{k_y}{2}\right]\right]}.$$
(30)
(+ for the antibonding and - for the bonding band) and the Cu amplitudes

$$\phi ^{(\pm )}(𝐤,0)=\frac{1}{N_\mathrm{\Lambda }}\sqrt{\frac{ϵ^{(\pm )}ϵ_p}{\left(2ϵ^{(\pm )}ϵ_p\right)}},$$
(31)
while the O amplitudes are obtained from

$$\left(ϵ_pϵ_𝐤^{(\pm )}\right)\phi ^{(\pm )}(𝐤,𝐚)+2t_{pd}\mathrm{cos}\left[\frac{k_y}{2}\right]\phi ^{(\pm )}(𝐤,0)=0,$$
(32)
and

$$\left(ϵ_pϵ_𝐤^{(\pm )}\right)\phi ^{(\pm )}(𝐤,𝐛)+2t_{pd}\mathrm{cos}\left[\frac{k_x}{2}\right]\phi ^{(\pm )}(𝐤,0)=0.$$
(33)
To write $`W_{\mathrm{Hubbard}}`$ in terms of the $`c_{𝐤\sigma }^{(\nu )^{}}`$ we must invert Eq.(28): $`c_{s\sigma }^{}=_{𝐤\nu }c_{𝐤\sigma }^{(\nu )^{}}\psi ^{(\nu )^{}}(𝐤,s)`$. Thus,

$$W_{\mathrm{Hubbard}}=\underset{𝐤_1..𝐤_4}{}\underset{\nu _1..\nu _4}{}U^{(\nu _1..\nu _4)}(𝐤_1,𝐤_3,𝐤_2,𝐤_4)c_{𝐤_1}^{(\nu _1)^{}}c_{𝐤_2}^{(\nu _2)}c_{𝐤_3}^{(\nu _3)^{}}c_{𝐤_4}^{(\nu _4)}.$$
(34)
Using a shorthand notation, where the band indices are understood,

$$U(𝐤_1,𝐤_3,𝐤_2,𝐤_4)=\underset{𝐫}{}e^{i(𝐤_1+𝐤_3𝐤_2𝐤_4)𝐫}\underset{s\mathrm{cell}}{}U_s\phi ^{}(𝐤_1,s)\phi ^{}(𝐤_3,s)\phi (𝐤_2,s)\phi (𝐤_4,s),$$
(35)
where $`_{s\mathrm{cell}}`$ involves a sum over a single cell. The umklapp processes involving the basis vectors of the reciprocal lattice produce a minus sign on one of the Oxygens. The matrix elements (35) are proportional to $`N_\mathrm{\Lambda }^2`$, like any bona fide two-body interaction.

The one-band Hubbard Model is even more elementary; we postpone the details to the next Section.

### B $`W=0`$ pairs and Superconducting Flux Quantization

In this Section we demonstrate that $`W=0`$ pairs with vanishing momentum and formed by holes in degenerate states exist whatever is their energy. Thus, in the thermodinamic limit, there are no constraints on the occupation number; any even number is “magic”. Instead of using the $`W=0`$ theorem and the full symmetry, that would in principle yield all the $`W=0`$ pairs, we follow the simpler route of projecting a single determinantal state on the irreps of $`C_{4v}`$ . This partial use of the symmetry still gives enough solutions to demonstrate pairing.

Let us first consider the Hubbard Model with three bands. Omitting band indices again, we shall mean

$$|d[𝐤]=c_{𝐤,}^{}c_{𝐤,}^{}|0$$
(36)
to be a two-hole determinantal state derived from the $`𝐤`$ eigenfunctions. Since $`\phi (𝐤,s)=\phi (𝐤,s)`$, which is required by time-reversal symmetry, the combination $`|d[𝐤]+|d[𝐤]`$ is singlet and $`|d[𝐤]|d[𝐤]`$ is triplet.

We introduce the determinants $`|d[R𝐤]|d[𝐤_R],RC_{4v}`$, and the projected states

$$|\mathrm{\Phi }_\eta \left[𝐤\right]=\frac{1}{\sqrt{8}}\underset{RC_{4v}}{}\chi ^{\left(\eta \right)}\left(R\right)|d[𝐤_R]$$
(37)
where $`\chi ^{\left(\eta \right)}(R)`$ is the character of the operation $`R`$ in the irreducible representation $`\eta `$. In the non-degenerate irreps, the operations that produce opposite $`𝐤_R`$ have the same character, and the corresponding projections lead to singlets. Let $`R_i,i=1,\mathrm{..8}`$ denote the operations of $`C_{4v}`$ and $`𝐤,𝐤^{}`$ any two vectors in the Brillouin Zone (BZ). Consider any two-body operator $`\widehat{O}`$, which is symmetric ($`R_i^{}\widehat{O}R_i=\widehat{O}`$), and the matrix with elements $`O_{i,j}=d[𝐤]|R_i^{}\widehat{O}R_j|d[𝐤^{}]`$, where $`𝐤`$ and $`𝐤^{}`$ may be taken to be in the same or in different bands. This matrix can be diagonalized by Group Theory alone. Indeed, for each irrep $`\eta `$, consider the normalized vector with components $`\frac{1}{\sqrt{8}}\chi ^{\left(\eta \right)}\left(R_i\right)`$; this is an eigenvector of the operator matrix $`R_i^{}\widehat{O}R_j`$, as we can check by noting that $`\frac{1}{8}_{i,j}\chi ^{\left(\eta \right)}\left(R_i\right)R_i^{}\widehat{O}R_j\chi ^{\left(\eta ^{}\right)}\left(R_j\right)=\widehat{O}P^{(\eta )^2}\delta (\eta ,\eta ^{})`$; hence, $`R_i^{}\widehat{O}R_j`$ is diagonal on the basis of the symmetry projected states. The square of the projection operator is $`P^{(\eta )^2}=\sqrt{8}P^{(\eta )}`$. Now, taking the matrix element between the $`𝐤`$ and $`𝐤^{}`$ determinants, we get the eigenvalues in terms of determinantal matrix elements:

$$O(\eta ,𝐤,𝐤^{})=\underset{R}{}\chi ^{\left(\eta \right)}\left(R\right)O_R(𝐤,𝐤^{})$$
(38)
where $`O_R(𝐤,𝐤^{})=d[𝐤|\widehat{O}|d[𝐤_R^{}]`$. If $`\widehat{O}`$ is identified with $`W_{\mathrm{Hubbard}}`$, the determinantal matrix element does not depend on the sign of the components of $`𝐤^{}`$, because the $`\phi `$’s depend on $`𝐤`$ only through a cosine. The only thing that matters is that $`C_4^{(+)},C_4^{()},\sigma _+`$ and $`\sigma _{}`$ exchange $`k_x^{}`$ and $`k_y^{}`$, while the other operations leave them in place. Consequently, $`(W_{\mathrm{Hubbard}})_\mathrm{𝟏}`$ = $`(W_{\mathrm{Hubbard}})_{C_2}`$ = $`(W_{\mathrm{Hubbard}})_{\sigma _x}`$ = $`(W_{\mathrm{Hubbard}})_{\sigma _y}`$ and $`(W_{\mathrm{Hubbard}})_{C_4^{(+)}}`$ = $`(W_{\mathrm{Hubbard}})_{C_4^{()}}`$ = $`(W_{\mathrm{Hubbard}})_{\sigma _+}`$ = $`(W_{\mathrm{Hubbard}})_\sigma _{}`$. Therefore

$$W_{\mathrm{Hubbard}}\left({}_{}{}^{1}A_{2}^{}\right)=W_{\mathrm{Hubbard}}\left({}_{}{}^{1}B_{2}^{}\right)=0.$$
(39)
These are $`W=0`$ pairs, like those studied previously, but with an important change, since in the cluster calculations the symmetries of $`W=0`$ pairs were found to be $`{}_{}{}^{1}B_{2}^{}`$ and $`{}_{}{}^{1}A_{1}^{}`$. The reason for this change is a twofold size effect. On one hand, $`{}_{}{}^{1}A_{1}^{}`$ pairs have the $`W=0`$ property only in the small clusters, having the topology of a cross, and belonging to the $`\mathrm{\Pi }_4`$ Group, but do not generalize as such to the full plane, when the symmetry is lowered to $`C_{4v}`$; on the other hand, the small clusters admit no solutions of $`{}_{}{}^{1}A_{2}^{}`$ symmetry at all if only degenerate states are used. One necessary condition for pairing in clusters is that the least bound holes form such a pair, and this dictates conditions on the occupation number. In the full plane, however, $`W=0`$ pairs exist at the Fermi level for any filling.

Let us now explore what happen if a magnetic field is turned on. Consider the pattern of Figure 8 (A).

Here, the Copper sites are marked by X and the Oxygen sites by O; the black dots stand for tubes carrying flux $`\varphi `$ each, symmetrically disposed around the central Cu. Varying $`\varphi `$ by an integer multiple of $`\varphi _0`$ corresponds to a gauge transformation leaving all the physical properties invariant. The arrows help to visualise a convenient choice of the vector potential at general $`\varphi `$. Namely, running along an oriented bond in the sense of the arrow,

$$_{}𝐀𝑑𝐫=\frac{\varphi }{2};$$
(40)
along the other Cu-O bonds, not marked in the figure, $`𝐀𝑑𝐫=0`$. One sees that in this way the flux through any closed path corresponds to the number of tubes surrounded by the path. The reflection operations of $`C_{4v}`$ are equivalent to $`\varphi \varphi `$, reverse the directions of the arrows and for a generic $`\varphi `$ the symmetry Group reduces to $`𝐙_4`$. However, at $`\varphi =\varphi _0/2`$ the reversal of the magnetic field in the tubes corresponds to a jump by $`\varphi _0`$, and this is equivalent to a gauge transformation: this implies that the symmetry Group gets bigger, the new symmetry operations being reflections supplemented by a gauge transformation. Indeed, it follows from Eq.(40) that the hopping parameter becomes $`it_{pd}`$ along the arrows, while it remains equal to $`t_{pd}`$ along the unmarked bonds of Figure 8 (A). Any reflection operation simply changes the signs of all the hoppings along the marked bonds. Now consider the unitary transformation $`𝒰`$ which changes the signs of all the Cu orbitals along both diagonal, except the central Cu. Since $`𝒰`$ also has the effect of reversing all the arrows, $`\sigma 𝒰`$ is a symmetry, for all reflections $`\sigma `$ in $`C_{4v}`$. Moreover, since the product of two reflections is a rotation, the Group $`\stackrel{~}{C}_{4v}`$ including the rotations and the reflections multiplied by $`𝒰`$ is isomorphic to $`C_{4v}`$. The $`W=0`$ pairs appropriate for half a flux quantum must involve two holes belonging to the degenerate irrep of $`\stackrel{~}{C}_{4v}`$. In this way, at $`\varphi =\varphi _0/2`$ the full symmetry is restored, allowing again for pairing and negative $`\mathrm{\Delta }`$. The $`W=0`$ quasiparticles have just the correct symmetry properties in the presence of the vector potential to provide superconducting flux quantisation in macroscopic systems.

$`W=0`$ pairs exist only in planar lattice structure with a certain point symmetry Group. So we expect that the CuO2 geometry is not the only one where $`W=0`$ property is present. In the following we want to show that in the one-band Hubbard Model too, where the point symmetry Group is still $`C_{4v}`$, we can build $`W=0`$ pairs and that they continue to exist even in the presence of magnetic field if and only if the magnetic flux is quantized in units of $`\varphi _0/2`$.

Let us start with the one-body Hamiltonian defined on a square lattice with $`N_\mathrm{\Lambda }\times N_\mathrm{\Lambda }`$ sites†††††† Although we know that the actual cuprate superconductors present a band structure with three dominant bands, the one-band Hubbard Model tries to mimic the presence of the charge transfer gap $`\mathrm{\Delta }_{pd}`$ by means of an effective value of the Coulomb repulsion and thus it presents only two bands. The “Oxygen” band becomes the lower Hubbard band of this model. (for the moment we don’t care of the spin index),

$$K=\frac{t}{2}\underset{𝐫,𝐫^{}}{}(c_𝐫^{}c_𝐫^{}+\mathrm{h}.c.)+ϵ\underset{𝐫}{}c_𝐫^{}c_𝐫,𝐫=(i_x,i_y),i_x,i_y=1,\mathrm{},N_\mathrm{\Lambda }$$
(41)
where $`𝐫,𝐫^{}`$ stands for nearest neighbors. We take the $`x,y`$ axes parallel to the bonds and fold the plane on itself after $`N_\mathrm{\Lambda }`$ lattice spacings in both directions, forming the torus shown in Figure 8 (B). Since we are dealing with complex fermion fields, the most general boundary conditions are

$$c_{𝐫+\tau _a}=e^{i\alpha }c_𝐫c_{𝐫+\tau _b}=e^{i\beta }c_𝐫$$
(42)
where $`\tau _a`$ and $`\tau _b`$ are the torus periods: $`\tau _a=(N_\mathrm{\Lambda },0)`$ and $`\tau _b=(0,N_\mathrm{\Lambda })`$. The fermion fields can then be expanded as

$$c_𝐫=\frac{1}{N_\mathrm{\Lambda }}\underset{𝐤}{}e^{i(𝐤+𝐭)𝐫}c_𝐤,𝐤=\frac{2\pi }{N_\mathrm{\Lambda }}(i_x,i_y),i_x,i_y=1,\mathrm{},N_\mathrm{\Lambda }$$
(43)
with $`𝐭=(\alpha /N_\mathrm{\Lambda },\beta /N_\mathrm{\Lambda })`$. Turning on a costant magnetic field $`𝐁=(B_a,B_b)`$ parallel to the surface of the torus, the flux through a circular surface $`\mathrm{\Sigma }_a`$ ($`\mathrm{\Sigma }_b`$) of radius $`r_0=N_\mathrm{\Lambda }/2\pi `$ perpendicular to the $`b`$ ($`a`$) direction will be

$$\varphi _\tau =_{\mathrm{\Sigma }_\tau }𝐁𝐧𝑑\sigma =_{\mathrm{\Sigma }_\tau }𝐀𝑑𝐥=2\pi r_0A_\tau ,\tau =a,b$$
(44)
with $`𝐧`$ the surface versor. The above equation enables us to compute, using the Peierls prescription, how the presence of this particular constant magnetic field changes the original Hamiltonian $`K`$ of Eq.(41). The final result is

$$K\frac{t}{2}[\underset{𝐫,𝐫^{}_a}{}(e^{\frac{2\pi i}{N_\mathrm{\Lambda }}(\varphi _a/\varphi _0)}c_𝐫^{}c_𝐫^{}+\mathrm{h}.c.)+\underset{𝐫,𝐫^{}_b}{}(e^{\frac{2\pi i}{N_\mathrm{\Lambda }}(\varphi _b/\varphi _0)}c_𝐫^{}c_𝐫^{}+\mathrm{h}.c.)]+ϵ\underset{𝐫}{}c_𝐫^{}c_𝐫$$
(45)
where $`𝐫,𝐫^{}_\tau `$ are two nearest neighbor sites along the $`\tau =a,b`$ direction. The spectrum of the new Hamiltonian is the same of the original one if $`\alpha \alpha +2\pi \varphi _a/\varphi _0`$ and $`\beta \beta +2\pi \varphi _b/\varphi _0`$. In this sense we can say that a change in boundary conditions is the same of turning on gauge fields. Of course the choice which physically corresponds to the unperturbed infinite plane is $`\alpha =\beta =0`$ (Born-von Karman boundary conditions).

Denoting with

$$e^{i\beta }\begin{array}{c}e^{i\alpha }\\ \begin{array}{c}\end{array}\\ \varphi _a\end{array}\varphi _b$$
(46)
the configuration for which the boundary conditions are $`e^{i\alpha }`$ and $`e^{i\beta }`$ and the flux is $`\varphi _a`$ and $`\varphi _b`$ along the the $`a`$ and $`b`$ direction respectively, explicit calculations show that for the Hamiltonian (45), $`W=0`$ pairs builded from determinantal states of the form in Eq.(36) of $`{}_{}{}^{1}A_{2}^{}`$, $`{}_{}{}^{1}B_{2}^{}`$ and $`{}_{}{}^{1}B_{1}^{}`$ symmetry exist if and only if one of the following configurations is realized

$$e^{i\beta }\begin{array}{ccc}e^{i\alpha }& & \\ \begin{array}{c}\end{array}& & \\ (n_\alpha \alpha /\pi )\varphi _0/2& & \end{array}(n_\beta \beta /\pi )\varphi _0/2$$
(47)
with $`n_\alpha `$ and $`n_\beta `$ integers such that $`(1)^{n_\alpha }=(1)^{n_\beta }`$.

From Eq.(47) we see that only two configurations allow for $`W=0`$ pairs in absence of magnetic field; they correspond to choose boundary conditions both periodic or antiperiodic along two orthogonal directions. With such boundary conditions $`W=0`$ pairs exist even in a magnetic field if and only if the flux is quantised in multiples of half the fundamental fluxon. For any other choice of boundary conditions, flux is still quantised in a similar manner, but we need a zero point flux in order to have $`W=0`$ pairs, so that they do not exist at zero magnetic field. If we assume dressed $`W=0`$ pairs to be quasiparticles of the superconducting phase, then flux is quantized in a superconducting way. In the next Section we will prove rigorously that this is the case, by studying the role of $`W=0`$ pairs in the many-body problem and showing how they become a genuine bound state by means of the electronic correlation.

### C Canonical Transformation

In the Cooper theory, an effective interaction involving phonons is introduced via an approximate canonical transformation. In the Hubbard Model, the holes can exchange particle-hole pairs, and more complex electronic excitations, rather than phonons, but one can approach the problem in a similar way.

Suppose the system is in its ground state with Fermi energy $`ϵ_F`$ and a couple of extra holes are added. We wish to show that by a canonical transformation one obtains an effective Hamiltonian which describes the propagation of a pair of dressed holes, and includes all many-body effects. Including all the diagrams of a generalized RPA would lead to something like the FLEX approximation  whose implications for the superconductivity in the three-band Hubbard Model have been explored recently in a series of papers. A related self-consistent and conserving T-matrix approximation has been proposed by Dahm and Tewordt for the excitation spectra in the $`2d`$ Hubbard Model; we mention incidentally that recently diagrammatic methods have been successfully applied to the photoelectron spectra of the cuprates in other contexts too, like the spin-fermion model.

The exact many-body ground state with two added holes may be expanded in terms of excitations over the vacuum (the non-interacting Fermi sphere) by a configuration interaction:

$$|\mathrm{\Psi }_0(N+2)=\underset{m}{}a_m|m+\underset{\alpha }{}a_\alpha |\alpha +\underset{\beta }{}a_\beta |\beta +\mathrm{}.$$
(48)
here $`m`$ runs over pair states, $`\alpha `$ over 4-body states ($`2`$ holes and $`1`$ e-h pair), $`\beta `$ over 6-body ones ($`2`$ holes and $`2`$ e-h pairs), and so on‡‡‡‡‡‡Many configurations contribute to the interacting ground state and we need a complete set to expand it exactly. However, as long as the set is complete, the expansion is exact and well defined only if the non-interacting ground state is non-degenerate. We assume this is the case in Eq.(48). Besides, we stress that Eq.(48) is configuration interaction, not a perturbative expansion.. To set up the Schrödinger equation, we consider the effects of the operators on the terms of $`|\mathrm{\Psi }_0(N+2)`$. We write:

$$K|m=ϵ_m|m,K|\alpha =ϵ_\alpha |\alpha ,K|\beta =ϵ_\beta |\beta ,\mathrm{}$$
(49)
and since $`W_{\mathrm{Hubbard}}`$ can create or destroy up to 2 e-h pairs,

$$W_{\mathrm{Hubbard}}|m=\underset{m^{}}{}W_{m^{},m}|m^{}+\underset{\alpha }{}W_{\alpha ,m}|\alpha +\underset{\beta }{}W_{\beta ,m}|\beta .$$
(50)
$`W_{m^{},m}`$ does not contribute to the effective interaction for $`W=0`$ pairs in our model; however we keep it for the sake of generality. It allows to introduce the effect of the exchange of phonons and other quasiparticles that we are not considering. For clarity let us first write the equations that include explicitly up to 6-body states; then we have

$$W_{\mathrm{Hubbard}}|\alpha =\underset{m}{}W_{m,\alpha }|m+\underset{\alpha ^{}}{}W_{\alpha ^{},\alpha }|\alpha ^{}+\underset{\beta }{}W_{\beta ,\alpha }|\beta $$
(51)
where scattering between 4-body states is allowed by the second term, and

$$W_{\mathrm{Hubbard}}|\beta =\underset{m^{}}{}W_{m^{},\beta }|m^{}+\underset{\alpha }{}W_{\alpha ,\beta }|\alpha +\underset{\beta ^{}}{}W_{\beta ^{},\beta }|\beta ^{}.$$
(52)
In principle, the $`W_{\beta ^{},\beta }`$ term can be eliminated by taking linear combinations of the complete set of $`\beta `$ states such that $`(K+W_{\mathrm{Hubbard}})_{\beta ^{},\beta }=ϵ_\beta ^{}\delta _{\beta \beta ^{}}`$: when this is done, we get a “self-energy” correction to $`ϵ_\beta `$ and a mixing of the vertices, without altering the structure of the equations. The Schrödinger equation yields equations for the coefficients $`a_m`$, $`a_\alpha `$ and $`a_\beta `$

$$\left(ϵ_mE_0\right)a_m+\underset{m^{}}{}W_{m,m^{}}a_m^{}+\underset{\alpha }{}W_{m,\alpha }a_\alpha +\underset{\beta }{}W_{m,\beta }a_\beta =0$$
(53)
$$\left(ϵ_\alpha E_0\right)a_\alpha +\underset{m^{}}{}W_{\alpha ,m^{}}a_m^{}+\underset{\alpha ^{}}{}W_{\alpha ,\alpha ^{}}a_\alpha ^{}+\underset{\beta }{}W_{\alpha ,\beta }a_\beta =0$$
(54)
$$\left(ϵ_\beta ^{}E_0\right)a_\beta +\underset{m^{}}{}W_{\beta ,m^{}}a_m^{}+\underset{\alpha ^{}}{}W_{\beta ,\alpha ^{}}a_\alpha ^{}=0$$
(55)
where $`E_0`$ is the interacting ground state energy. Then, we exactly decouple the 6-body states by solving the equation for $`a_\beta `$ and substituting into Eqs.(53)(54), getting:

$$\left(ϵ_mE_0\right)a_m+\underset{m^{}}{}\left[W_{m,m^{}}+\underset{\beta }{}\frac{W_{m,\beta }W_{\beta ,m^{}}}{E_0ϵ_\beta ^{}}\right]a_m^{}+\underset{\alpha }{}\left[W_{m,\alpha }+\underset{\beta }{}\frac{W_{m,\beta }W_{\beta ,\alpha }}{E_0ϵ_\beta ^{}}\right]a_\alpha =0$$
(56)
$$\left(ϵ_\alpha E_0\right)a_\alpha +\underset{m^{}}{}\left[W_{\alpha ,m^{}}+\underset{\beta }{}\frac{W_{\alpha ,\beta }W_{\beta ,m^{}}}{E_0ϵ_\beta ^{}}\right]a_m^{}+\underset{\alpha ^{}}{}\left[W_{\alpha ,\alpha ^{}}+\underset{\beta }{}\frac{W_{\alpha ,\beta }W_{\beta ,\alpha ^{}}}{E_0ϵ_\beta ^{}}\right]a_\alpha ^{}=0$$
(57)
Thus we see that the rôle of 6-body states is just to renormalize the interaction between 2-body and 4-body ones, and for the rest they may be forgotten. If $`E_0`$ is outside the continuum of excitations, as we shall show in the next Section, the corrections are finite, and experience with clusters suggests that they are small. Had we included 8-body excitations, we could have eliminated them by solving the system for their coefficients and substituting, thus reducing to the above problem with further renormalizations. In principle, the method applies to all the higher order interactions, and we can recast our problem as if only 2 and 4-body states existed. Again, the $`W_{\alpha ^{},\alpha }`$ term can be eliminated by taking linear combinations of the $`\alpha `$ states: when this is done, we get a “self-energy” correction to $`ϵ_\alpha `$ and a mixing of the $`W_{m,\alpha }`$ vertices. Denoting $`W^{}`$ and $`ϵ^{}`$ the renormalised quantities, which can be determined by the procedure outlined above, one can solve for $`a_\alpha `$. The eigenvalue problem becomes

$$\left(E_0ϵ_m\right)a_m=\underset{m^{}}{}\left\{W_{m,m^{}}^{}+m|S[E_0]|m^{}\right\}a_m^{},$$
(58)
where

$$m|S\left[E_0\right]|m^{}=\underset{\alpha }{}\frac{m|W^{}|\alpha \alpha |W^{}|m^{}}{E_0ϵ_\alpha ^{}}.$$
(59)
Eq.(58) is of the form of a Schrödinger equation with eigenvalue $`E_0`$ for pairs with an effective interaction $`W^{}+S`$. Then we interpret $`a_m`$ as the wave function of the dressed pair, which is acted upon by an effective Hamiltonian $`\stackrel{~}{H}_{\mathrm{pair}}`$. This way of looking at Eq.(58) is perfectly consistent, despite the presence of the many-body eigenvalue $`E_0`$, because we are not compelled to reference the energy eigenvalues to the hole vacuum. We note that if we shift the kinetic operator $`K`$ by an arbitrary constant $`\mathrm{\Delta }E`$ in Eq.(49), by setting $`K^{}=K\mathrm{\Delta }E`$, the same shift applies to the eigenvalues $`ϵ_m,ϵ_\alpha ,ϵ_\beta `$ and so on, and also to the renormalised quantities like $`ϵ_\alpha ^{},ϵ_\beta ^{}`$. Therefore, the matrix elements of the scattering operator $`S`$ are unaffected by the shift. Thus we can reference $`E_0`$ to a new energy origin by shifting the diagonal terms in Eq.(58) without changing the off-diagonal terms. Since we wish to regard Eq.(58) as a Cooper-like equation for the pair, it is natural to set $`\mathrm{\Delta }E`$ equal to the interacting ground state energy eigenvalue for the $`N`$ hole system, relative to the hole vacuum. The energy of two independent holes, relative to the $`N`$ background, is $`2ϵ_F`$; when the effective interaction is accounted for, the energy of the two bound holes is $`2ϵ_F+\mathrm{\Delta }`$, where $`|\mathrm{\Delta }|`$ is the binding energy.

The change from the full many-body $`H_{\mathrm{Hubbard}}`$ to $`\stackrel{~}{H}_{\mathrm{pair}}`$ is the canonical transformation to dressed pairs we were looking for. In the new picture, the holes interact through an effective vertex with infinitely many contributions. The linked contributions represent repeated exchange of electron-hole pairs, and may contain self-energy insertions; all these contributions make up the effective interaction. The unlinked diagrams are pure self-energy. Thus, the scattering operator $`S`$ is of the form $`S=W_{\mathrm{eff}}+F`$, where $`W_{\mathrm{eff}}`$ is the effective interaction between dressed holes, while $`F`$ is a forward scattering operator, diagonal in the pair indices $`m`$ ,$`m^{}`$ which accounts for the self-energy corrections of the one-body propagators: it is evident from Eq.(58) that it just redefines the dispersion law $`ϵ_m`$ and we suppose it be included in the kinetic term $`K`$.

So, letting $`|a=_ma_m|m`$, the effective Schrödinger equation for the pair reads

$$\left(K+W^{}+W_{\mathrm{eff}}\right)|a=E_0|a$$
(60)
and pairing takes place if $`E_0=2ϵ_F|\mathrm{\Delta }|`$; then $`|\mathrm{\Delta }|`$ is the binding energy of the pair. Any other pairing mechanism not considered here, like off-site interactions, inter-planar coupling and phonons, can be included as an extra contribution to $`W_{m^{},m}^{}`$ which just adds to $`W_{\mathrm{eff}}`$.

We emphasized the fact that in principle the canonical transformation is exact because in this way the framework does not require $`U/t`$ to be small. However to test the instability of the Fermi liquid towards pairing it is sufficient to study the amplitudes $`a_m`$ of the $`m`$ states. In the weak coupling limit this can be done truncating the expansion (48) to the $`\alpha `$ states because, as we have shown, the inclusion of the $`\beta ,\gamma ,\mathrm{}`$ states produces a renormalization of the matrix elements of higher order in $`U`$, leaving the structure of the equations unaltered\**\**\** We want to stress that the truncated expansion of $`|\mathrm{\Psi }_0(N+2)`$ in Eq.(48) doesn’t give a good approximation of the interacting ground state wave function but only of its weak coupling $`a_m`$ amplitudes. Similarly in the BCS Model, from the Cooper equation (obtained by truncating $`|\mathrm{\Psi }_0(N+2)`$ to the $`m`$ states) we can estimate only the pair coefficients of the ground state and not its full structure. Nevertheless this is enough to study bound states formation; indeed the energy gap of the pair in the Cooper theory and in the many-body BCS theory are identical. Moreover, the pair wave function of the Cooper Model resembles the one of the many-body BCS Model..

Let $`|\mathrm{\Phi }_0(N)`$ be the non-interacting ground state formed by filling all the energy levels up to $`ϵ_F(N)`$ for both spin up and down. If the added pair has vanishing total momentum, like the one in Eq.(36), the $`\alpha `$ states are

$$|\alpha =c_{𝐤^{}+𝐪+𝐤_2,}^{}c_{𝐤_2,}c_{𝐪,}^{}c_{𝐤^{},}^{}|\mathrm{\Phi }_0(N)$$
(61)
where $`c_{𝐤_2,}`$ creates an electron state; hence $`ϵ_{𝐤_2}<ϵ_F<ϵ_{𝐤^{}+𝐪+𝐤_2}`$, $`ϵ_𝐪`$, $`ϵ_𝐤^{}`$. The $`\alpha `$ states with opposite spin indices arise from the specular diagram, contribute similarly and yield a factor of 2 at the end. The interaction matrix element is

$`\mathrm{\Phi }_0(N)|c_{𝐤^{},}c_{𝐪,}c_{𝐤_2,}^{}c_{𝐤^{}+𝐪+𝐤_2,}W_{\mathrm{Hubbard}}|d[𝐤]=`$ (62)
$`\delta (𝐪𝐤)U(𝐤^{}+𝐪+𝐤_2,𝐤^{},𝐤,𝐤_2)\delta (𝐤^{}𝐤)U(𝐤^{}+𝐪+𝐤_2,𝐪,𝐤,𝐤_2)`$ (63)
where the $`U`$ matrix is computed on the Bloch basis, see Section III A. This expression holds for any lattice with translational invariance. Working out Eq.(59) we find that the product in the numerator yields 4 terms; two are proportional to $`\delta (𝐩𝐪)`$ and belong to $`F`$, while the cross terms yield identical contributions to $`W_{\mathrm{eff}}`$. Thus we obtain the following effective interaction between the members of $`W=0`$ pairs:

$`\mathrm{\Phi }_\eta \left[𝐩\right]\left|W_{\mathrm{eff}}\right|\mathrm{\Phi }_\eta \left[𝐪\right]=4{\displaystyle \underset{RC_{4v}}{}}\chi ^{(\eta )}(R){\displaystyle \underset{𝐤D(ϵ_F)}{}}\theta (ϵ_{𝐩+𝐪_R+𝐤}ϵ_F)\times `$ (64)
$`\times {\displaystyle \frac{U(𝐩+𝐪_R+𝐤,𝐩,𝐪_R,𝐤)U(𝐩,𝐤,𝐩+𝐪_R+𝐤,𝐪_R)}{ϵ_{𝐩+𝐪_R+𝐤}ϵ_𝐤+ϵ_𝐪+ϵ_𝐩E_0}},`$ (65)
while it can be shown that the corresponding matrix elements of the forward scattering operator $`F`$ vanish identically as in the fully symmetric clusters. The sum in Eq.(65) is over occupied $`𝐤`$ with empty $`𝐩+𝐪_R+𝐤`$. Note that $`W_{\mathrm{eff}}`$ does not depend on the sign of $`U`$. The diagonal elements of Eq.(65) are also clearly related to the $`\mathrm{\Delta }^{\left(2\right)}`$ expression (20) derived from perturbation theory for the fully symmetric clusters, which are special cases of the present theory. The expressions (20) and (65) are characterized by the symmetry-induced quantum mechanical interference of several terms. The sum can be positive or negative depending on the irrep. This interference produces a partial cancellation, and the absolute value of the result is typically much smaller than individual contributions. This explains why the interaction is dynamically small for $`W=0`$ pairs: they have no direct interaction, and because of the interference the effective interaction is reduced compared to what one could expect by a rough order-of-magnitude estimate. However, the presence of the $`\theta `$ functions and the anisotropy of the integrands prevent a total cancellation.

In Eq.(20), the vanishing of the denominators is prevented by the discrete spectrum of the cluster. In the thermodynamic limit this complication disappears in the full expression (65) since we are interested in bound pairs; then, $`E_0`$ is below the continuum and the denominators never vanish.

The $`𝐩`$ and $`𝐪`$ indices run over $`1/8`$ of the empty BZ for $`W=0`$ pairs. We denote such a set of empty states $`D(ϵ_F)/8`$, and cast the result in the form of a (Cooper-like) Schrödinger equation

$$2ϵ_𝐤a_𝐤+\underset{𝐤^{}D(ϵ_F)/8}{}W_{\mathrm{eff}}(𝐤,𝐤^{})a_𝐤^{}=E_0a_𝐤$$
(66)
for a self-consistent calculation of $`E_0`$ (since $`W_{\mathrm{eff}}`$ depends on the solution).

### D Pairing in the CuO2 Plane: Numerical Results

Using the analytical expression for the effective interaction in the full plane, Eq.(65), we have performed exploratory numerical estimates of $`\mathrm{\Delta }`$ by working on supercells of $`N_\mathrm{\Lambda }\times N_\mathrm{\Lambda }=|\mathrm{\Lambda }|/3`$ cells, with periodic boundary conditions. For the sake of simplicity, we shall neglect the minor contributions from the higher bands and consider the dominant intra-band processes, in which empty states belong to the bonding band. Here we solved the problem in a virtually exact way for $`N_\mathrm{\Lambda }`$ up to 40. Several good supercell calculations devoted to the problem of pairing have been reported to date, but no conclusive evidence was reached, because of the difficulty of dealing with size effects. First, we searched for triplet solutions with negative energy without success, since, as in the clusters, $`W_{\mathrm{eff}}`$ is repulsive for triplets. On the contrary, $`W=0`$ singlets did show pairing, in line with our previous findings in small clusters. We took as input data the set of current parameters, already used for clusters, that is (in eV) $`t_{pd}=1.3`$, $`ϵ_p=3.5`$, $`ϵ_d=0`$, $`U_p=6s`$, $`U_d=5.3s`$, where $`s`$ is a scale factor induced by renormalization. Since screening excitations are explicitly accounted for in the Hamiltonian, it is likely that $`U`$ is a bare (unscreened) quantity, which justifies $`s>1`$. A stronger interaction causes smaller pairs and speeds up convergence within attainable supercell sizes. In Table VI, we report the results for $`{}_{}{}^{1}B_{2}^{}`$ pairs at $`s=\frac{3}{\sqrt{2}}=2.121`$ with $`ϵ_F=1.3`$ eV (half filling corresponds to $`ϵ_F=1.384`$ eV). We see that although $`|\mathrm{\Delta }|`$ decreases monotonically with increasing supercell size, $`V_{\mathrm{eff}}`$, see below for its definition, is not dropping to zero, but remains fairly stable around 6 to 7 eV.

With supercell sizes $`N_\mathrm{\Lambda }>40`$ calculations become hard. Since we are concerned with the asymptotic behavior for $`N_\mathrm{\Lambda }\mathrm{}`$ and $`\mathrm{\Delta }`$ depends on $`U`$’s and $`N_\mathrm{\Lambda }`$ in a peculiar way, increasing with $`N_\mathrm{\Lambda }`$ for large $`U`$’s and dropping for small $`U`$’s, we need a simple solvable model in supercells and in the infinite plane to make reliable extrapolations of numerical results. To this end, we define the Uniform Interaction Model (UIM) in which a constant negative interaction $`V_{\mathrm{eff}},V_{\mathrm{eff}}>0`$ prevails for $`𝐤`$ and $`𝐤^{}`$ in $`D(ϵ_F)/8`$. In the Cooper formula for the binding energy of the pair one has

$$|\mathrm{\Delta }|=\frac{2\omega _D}{e^{\frac{1}{\gamma \rho _F}}1},$$
(67)
where $`\rho _F`$ is the density of states at the Fermi level and $`\gamma `$ is a (constant) attractive interaction per cell in a shell of thickness $`2\omega _D`$ surrounding the Fermi surface (the orders of magnitude are $`\omega _D25`$ meV, $`\rho _F0.3`$ eV-1/cell and $`\gamma 1`$ eV/cell, and $`|\mathrm{\Delta }|`$ is in the meV range); on the other hand, in the UIM no Debye frequency $`\omega _D`$ is involved, and all the empty states in $`D(ϵ_F)/8`$ contribute to $`\mathrm{\Delta }`$. Both the Cooper and the UIM models can be solved in supercell calculations, and show the same qualitative behavior with increasing $`N_\mathrm{\Lambda }`$.

For small $`N_\mathrm{\Lambda }`$, $`\mathrm{\Delta }`$ is of the same order as $`V_{\mathrm{eff}}`$, while in the thermodynamic limit ($`N_\mathrm{\Lambda }\mathrm{}`$), the asymptotic value of $`\mathrm{\Delta }`$, $`\mathrm{\Delta }_{\mathrm{asympt}}`$, can easily be estimated. Setting $`W_{\mathrm{eff}}=V_{\mathrm{eff}}/N_\mathrm{\Lambda }^2`$, we get from Eq.(66)

$$(2ϵ_𝐤E_0)a_𝐤=\frac{V_{\mathrm{eff}}}{8}\frac{1}{(2\pi )^2}𝑑𝐤^{}a_𝐤^{}=\mathrm{const}.$$
(68)
Writing $`a_𝐤=\mathrm{c}onst/(2ϵ_𝐤E_0)`$ and $`E_0=2ϵ_F|\mathrm{\Delta }|`$, we obtain

$$\frac{8}{V_{\mathrm{eff}}}=_{ϵ_F}^0\frac{dϵ\rho \left(ϵ\right)}{2\left(ϵϵ_F\right)+|\mathrm{\Delta }_{\mathrm{asympt}}|}.$$
(69)
Here, $`\rho `$ is not a constant, as in the Cooper formula, and its values in the integration range are sensitive to filling; howewer its order of magnitude does not differ much from the BCS case except at half filling. Good fits can be obtain using the Cooper formula with effective $`\omega _D`$ and $`\rho _F`$ parameters, like those shown in Table VII.

In Table VIII, we consider $`{}_{}{}^{1}B_{2}^{}`$ pairs at $`ϵ_F=1.2`$ eV and report values of $`\mathrm{\Delta }`$ and $`V_{\mathrm{eff}}`$ for supercell calculations at $`N_\mathrm{\Lambda }`$=12, 20 and 30 for 3 values of the scale factor $`s`$. The filling is $`\rho 1.3`$ at $`N_\mathrm{\Lambda }=30`$. Fixing $`V_{\mathrm{eff}}`$ at the value of $`N_\mathrm{\Lambda }=30`$ we calculate $`\mathrm{\Delta }_{\mathrm{asympt}}`$ for $`N_\mathrm{\Lambda }\mathrm{}`$.

We see that the relatively mild $`N_\mathrm{\Lambda }`$ dependence of $`V_{\mathrm{eff}}`$ supports the use of the UIM to extrapolate the results to the thermodynamic limit, and there is a clear indication of pairing with sizable binding energies. The $`s`$ dependence of $`V_{\mathrm{eff}}`$ is roughly linear, while $`\mathrm{\Delta }`$ depends exponentially on $`s`$. Table IX presents the results for $`{}_{}{}^{1}B_{2}^{}`$ pairs at $`ϵ_F=1.1`$ eV ($`\rho 1.4`$ at $`N_\mathrm{\Lambda }=30`$). The trend is similar, but $`V_{\mathrm{eff}}`$ is seen to increase with doping.

The results for the $`{}_{}{}^{1}A_{2}^{}`$ pairs are seen to lead to bound states as well, with comparable $`\mathrm{\Delta }`$ values; the trend with doping is opposite, however, and the gap is nearly closing at $`ϵ_F=1.1`$ eV. A necessary condition for superconducting flux quantization is that two kinds of pairs of similar binding energy and different symmetries exist. A similar conclusion was reached independently by other authors. Moreover, evidence of mixed $`(s+id)`$ symmetry for the pairing state has been amply reported in angle-resolved photoemission studies . This remark leads to the prediction that in this model superconductive pairing disappears with increasing $`\rho `$, while a different sort of pairing prevails; in reality the CuO2 plane prefers to distort at excessive doping, and in a distorted plane the present mechanism, based on symmetry, could be destroyed.

### E Antiferromagnetic Ground State at Half Filling

Up to now, we learned how to master the situation when the number $`N`$ of holes in the $`N_\mathrm{\Lambda }\times N_\mathrm{\Lambda }`$ system is such that the non-interacting ground state $`|\mathrm{\Phi }_0(N)`$ is a single non-degenerate determinant (the Fermi surface is totally filled). Then, switching the repulsion $`W_{\mathrm{Hubbard}}`$ on, we know how to calculate the effective interaction $`W_{\mathrm{eff}}`$ between two extra holes added to the system by the expansion (48). However we are particularly interested in the doped antiferromagnet, and the antiferromagnetic ground state occurs at half filling, not in a filled-shell situation.

We want to study the doped antiferromagnet since there are strong indications that the Fermi liquid is unstable towards pairing near half filling; they come from diagrammatic approaches, renormalization group techniques and also cluster diagonalizations . Therefore exact results on the half filled Hubbard Model may be relevant to antiferromagnetism and to the mechanism of the superconducting instability as well. On the other hand, pairing by the “$`W=0`$” mechanism does not require that the pair be created on a single-determinant state.

For simplicity in the rest of this paper we concentrate on the one-band Hubbard Model, defined by Eq.(41) plus the usual on-site Hubbard interaction $`W_{\mathrm{Hubbard}}`$:

$$H_{\mathrm{Hubbard}}=K+W_{\mathrm{Hubbard}}=\frac{t}{2}\underset{𝐫,𝐫^{}\sigma }{}(c_{𝐫\sigma }^{}c_{𝐫^{}\sigma }+\mathrm{h}.c.)+U\underset{𝐫}{}\widehat{n}_𝐫\widehat{n}_𝐫$$
(70)
with $`𝐫=(i_x,i_y)`$, $`i_x,i_y=1,\mathrm{},N_\mathrm{\Lambda }`$, the sum on $`𝐫,𝐫^{}`$ is over the pairs of nearest neighbors sites and $`\widehat{n}_{𝐫\sigma }`$ is the number operator on the site $`𝐫`$ of spin $`\sigma `$\*†\*†\*†Here we have dropped the one-body on-site potential $`ϵ_{𝐫\sigma }c_{𝐫\sigma }^{}c_{𝐫\sigma }`$, since we work with a fixed number of spin up and down particles.. The point symmetry is $`C_{4v}`$; besides, $`H_{\mathrm{Hubbard}}`$ is invariant under the commutative Group of translations $`𝐓`$ and hence the space Group $`𝐆=𝐓C_{4v}`$; $``$ means the semidirect product. In terms of the Fourier expanded fermion operators (periodic boundary conditions) $`c_𝐤=\frac{1}{N_\mathrm{\Lambda }}_𝐫e^{i𝐤𝐫}c_𝐫`$, we have $`K=_𝐤ϵ_𝐤c_{𝐤\sigma }^{}c_{𝐤\sigma }`$ with $`ϵ_𝐤=2t[\mathrm{cos}k_x+\mathrm{cos}k_y]`$. Then, the one-body plane wave state $`c_{𝐤\sigma }^{}|0|𝐤\sigma `$ is an eigenstate of $`K`$.

The $`4\times 4`$ cluster is half filled at $`N=16`$. Below, we shall consider its ground state with $`N=4`$ and $`N=14`$ holes. For $`U0`$, $`N=4`$ means that 2 holes are added to a closed shell, while $`N=14`$ corresponds to 2 electrons added to the half filled system. We demonstrate that in both cases the structure of the ground state must be interpreted in terms of pairing\*‡\*‡\*‡Hole pairing in the former case and electron pairing in the latter.. However the non-interacting ground state at half filling is degenerate and in order to deal with $`N=14`$ we must extend the above formalism.

As a preliminary measure in this Section we build the exact ground state of the Hubbard Model at half filling and weak coupling for a general even $`N_\mathrm{\Lambda }`$. Once a unique non-interacting ground state is determined, one can use the non-perturbative canonical transformation to test the instability of the system towards pairing; this will be done in the next Section for $`N_\mathrm{\Lambda }=4`$.

The starting point is the following property of the number operator $`\widehat{n}_𝐫=c_𝐫^{}c_𝐫`$ (for the moment we omit the spin index).

Theorem: Let $`𝒮`$ be an arbitrary set of plane-wave eigenstates $`\{|𝐤_i\}`$ of $`K`$ and $`(n_𝐫)_{ij}=𝐤_i|\widehat{n}_𝐫|𝐤_j=\frac{1}{N_\mathrm{\Lambda }^2}e^{i(𝐤_i𝐤_j)𝐫}`$ the matrix of $`\widehat{n}_𝐫`$ in $`𝒮`$. This matrix has eigenvalues $`\lambda _1=\frac{|𝒮|}{N_\mathrm{\Lambda }^2}`$ and $`\lambda _2=\mathrm{}=\lambda _{|𝒮|}=0`$.

Note that $`|𝒮|N_\mathrm{\Lambda }^2`$; if $`|𝒮|=N_\mathrm{\Lambda }^2`$ the set is complete, like the set of all orbitals, and the theorem is trivial (a particle on site $`𝐫`$ is the $`\widehat{n}_𝐫`$ eigenstate with eigenvalue 1). Otherwise, if $`|𝒮|<N_\mathrm{\Lambda }^2`$, the theorem is an immediate consequence of the fact that

$$\mathrm{d}et|(n_𝐫)_{ij}\lambda \delta _{ij}|=(\lambda )^{|𝒮|1}(\frac{|𝒮|}{N_\mathrm{\Lambda }^2}\lambda ),𝐫.$$
(71)
Let $`𝒮_{hf}`$ denote the set (or shell) of the $`𝐤`$ wave vectors such that $`ϵ_𝐤=0`$. At half filling ($`N_\mathrm{\Lambda }^2`$ particles) for $`U=0`$ the $`𝒮_{hf}`$ shell is half occupied, while all $`𝐤`$ orbitals such that $`ϵ_𝐤<0`$ are filled. The $`𝐤`$ vectors of $`𝒮_{hf}`$ lie on the square having vertices $`(\pm \pi ,0)`$ and $`(0,\pm \pi )`$; one readily realizes that the dimension of the set $`𝒮_{hf}`$ is $`|𝒮_{hf}|=2N_\mathrm{\Lambda }2`$. Since $`N_\mathrm{\Lambda }`$ is even and $`H_{\mathrm{Hubbard}}`$ commutes with the total spin operators, at half filling every ground state of $`K`$ is represented in the $`S^z=0`$ subspace. Thus, $`K`$ has $`\left(\begin{array}{c}2N_\mathrm{\Lambda }2\\ N_\mathrm{\Lambda }1\end{array}\right)^2`$ degenerate unperturbed ground state configurations with $`S^z=0`$. We wish to study below how this degeneracy is removed by the Hubbard interaction $`W_{\mathrm{Hubbard}}`$ already in first-order perturbation theory. Actually most of the degeneracy is removed in first-order, and with the help of a theorem by Lieb we shall be able to single out the true, unique ground state of $`H_{\mathrm{Hubbard}}`$ in Eq.(70) The Lieb theorem states that at half filling the ground state for a bipartite lattice is unique and has spin $`||𝒮_1||𝒮_2||/2`$ where $`|𝒮_1|`$ ($`|𝒮_2|`$) is the number of sites in the $`𝒮_1`$ ($`𝒮_2`$) sublattice.. The first-order splitting of the degeneracy is obtained by diagonalizing the $`W_{\mathrm{Hubbard}}`$ matrix over the unperturbed basis; like in elementary atomic physics, the filled shells just produce a constant shift of all the eigenvalues and for the rest may be ignored in first-order calculations. In other terms we consider the truncated Hilbert space $``$ spanned by the states of $`N_\mathrm{\Lambda }1`$ holes of each spin in $`𝒮_{hf}`$, and we want the exact ground state(s) of $`W_{\mathrm{Hubbard}}`$ in $``$; by construction $``$ is in the kernel of $`K`$, so the ground state of $`W_{\mathrm{Hubbard}}`$ is the ground state of $`H_{\mathrm{Hubbard}}`$ as well. We call $`W=0`$ state any vector in $``$ which also belongs to the kernel of $`W_{\mathrm{Hubbard}}`$. Since the lowest eigenvalue of $`W_{\mathrm{Hubbard}}`$ is zero, it is evident that any $`W=0`$ state is a ground state of $`H_{\mathrm{Hubbard}}`$. We want to calculate the unique ground state of the Hubbard Hamiltonian for $`U=0^+`$ at half filling which is a $`W=0`$ singlet with $`2N_\mathrm{\Lambda }2`$ holes in $`𝒮_{hf}`$ (filled shells are understood)Equivalently, we shall find the exact $`(2N_\mathrm{\Lambda }2)`$-body ground state of the effective Hamiltonian
$$H_{\mathrm{eff}}=\frac{U}{N_\mathrm{\Lambda }^4}\underset{𝐤_1,𝐤_2,𝐤_3,𝐤_4𝒮_{hf}}{}\delta (𝐤_1+𝐤_2𝐤_3𝐤_4)c_{𝐤_1}^{}c_{𝐤_2}^{}c_{𝐤_3}c_{𝐤_4}$$
(72)  where $`\delta (G)=1`$ if $`G`$ is a reciprocal lattice vector and zero otherwise..

To diagonalize the local  operator $`W_{\mathrm{Hubbard}}`$ in closed form we need to set up a local  basis set of one-body states. If $`𝒮_{hf}`$ were the complete set of plane-wave states $`𝐤`$, the new basis would be trivially obtained by a Fourier transformation, but this is not the case. The question is: how can we define for each site $`𝐫`$ the local counterparts of $`𝐤`$ states using only those that belong to a degenerate level? The answer is: build a set $`\{|\phi _\alpha ^{(𝐫)}\}`$ of orbitals such that the number operator $`\widehat{n}_𝐫`$ and the Dirac characters of the point symmetry Group $`C_{4v}`$ are diagonal. Using such a basis set for the half-filled shell the unique properties of the antiferromagnetic ground state become simple and transparent. The eigenvectors $`|\phi _\alpha ^{(0)}`$ of $`n_{𝐫=0}`$ and those $`|\phi _\alpha ^{(𝐫)}`$ of other sites $`𝐫`$ are connected by translation and also by a unitary transformation, or change of basis set. Picking $`𝐫=\widehat{e}_l`$, $`l=x`$ means $`\widehat{e}_l=(1,0)`$ or transfer by one step towards the right and $`l=y`$ means $`\widehat{e}_l=(0,1)`$ or transfer by one step upwards. The unitary transformation reads:

$$|\phi _\alpha ^{(\widehat{e}_l)}=\underset{\beta =1}{\overset{2N_\mathrm{\Lambda }2}{}}|\phi _\beta ^{(0)}\phi _\beta ^{(0)}|\phi _\alpha ^{(\widehat{e}_l)}\underset{\beta =1}{\overset{2N_\mathrm{\Lambda }2}{}}|\phi _\beta ^{(0)}T_{l_{\beta \alpha }}.$$
(73)
The transfer matrix $`T_l`$ knows all the translational and point symmetry of the system, and will turn out to be very special.

For large $`N_\mathrm{\Lambda }`$, to find $`\{|\phi _\alpha ^{(𝐫)}\}`$ it is convenient to separate the $`𝐤`$’s of $`𝒮_{hf}`$ in irreducible representations of the space Group $`𝐆`$$`=C_{4v}𝐓`$. Choosing an arbitrary $`𝐤𝒮_{hf}`$ with $`k_xk_y0`$, the set of vectors $`R_i𝐤`$, where $`R_iC_{4v}`$, is a (translationally invariant) basis for an irrep of $`𝐆`$. The high symmetry vectors $`(0,\pi )`$ and $`(\pi ,0)`$ always trasform among themselves and are the basis of the only two-dimensional irrep of $`𝐆`$, which exists for any $`N_\mathrm{\Lambda }`$. If $`N_\mathrm{\Lambda }/2`$ is even, one also finds the high symmetry wavevectors $`𝐤=(\pm \pi /2,\pm \pi /2)`$ which mix among themselves and yield a four-dimensional irrep. In general, the vectors $`R_i𝐤`$ are all different, so all the other irreps of $`𝐆`$ have dimension 8, the number of operations of the point Group $`C_{4v}`$.

Next, we show how to build our local basis set and derive $`W=0`$ states for each kind of irreps of $`𝐆`$. For illustration, we will consider the case $`N_\mathrm{\Lambda }=4`$; then $`𝒮_{hf}`$ contains the bases of two irreps of $`𝐆`$, of dimensions 2 and 4. The one with basis $`𝐤_A=(\pi ,0),𝐤_B=(0,\pi )`$ breaks into $`A_1B_1`$ in $`C_{4v}`$.

The eigenstates of $`(n_{𝐫=0})_{ij}=𝐤_i|\widehat{n}_{𝐫=0}|𝐤_j`$, with $`i,j=A,B`$, are $`|\psi _{A_1}^{\prime \prime }=\frac{1}{\sqrt{2}}(|𝐤_A+|𝐤_B)`$ with $`\lambda _1=1/8`$ and $`|\psi _{B_1}^{\prime \prime }=\frac{1}{\sqrt{2}}(|𝐤_A|𝐤_B)`$ with $`\lambda _2=0`$. Since under translation by a lattice step $`T_l`$ along the $`l=x,y`$ direction $`|𝐤e^{ik_l}|𝐤`$, using Eq.(73) one finds that $`|\psi _{A_1}^{\prime \prime }(1)^{\theta _l^{\prime \prime }}|\psi _{B_1}^{\prime \prime }`$, with $`\theta _x^{\prime \prime }=1,\theta _y^{\prime \prime }=0`$; so $`|\psi _{A_1}^{\prime \prime }`$ has vanishing amplitude on a sublattice and $`|\psi _{B_1}^{\prime \prime }`$ on the other. The two-body state $`|\psi _{A_1}^{\prime \prime }_\sigma |\psi _{B_1}^{\prime \prime }_\sigma `$ has occupation for spin $`\sigma `$ but not for spin $`\sigma `$ on the site $`𝐫=0`$; under a lattice step translation it flips the spin and picks up a (-1) phase factor: $`|\psi _{A_1}^{\prime \prime }_\sigma |\psi _{B_1}^{\prime \prime }_\sigma |\psi _{B_1}^{\prime \prime }_\sigma |\psi _{A_1}^{\prime \prime }_\sigma `$; therefore it has double occupation nowhere and is a $`W=0`$ state ($`W=0`$ pair ).

The 4-dimensional irrep with basis $`𝐤_1=(\pi /2,\pi /2),𝐤_2=(\pi /2,\pi /2),𝐤_3=(\pi /2,\pi /2)𝐤_4=(\pi /2,\pi /2)`$ breaks into $`A_1B_2E`$ in $`C_{4v}`$; letting $`I=1,2,3,4`$ for the irreps $`A_1,B_2,E_x,E_y`$ respectively, we can write down all the eigenvectors of $`(n_{𝐫=0})_{ij}=𝐤_i|\widehat{n}_{𝐫=0}|𝐤_j`$, with $`i,j=1,\mathrm{},4`$, as $`|\psi _I^{}=_{i=1}^4O_{Ii}^{}|𝐤_i`$, where $`O^{}`$ is the following 4$`\times `$4 orthogonal matrix

$$O^{}=\frac{1}{2}\left[\begin{array}{cccc}\hfill 1& \hfill 1& \hfill 1& \hfill 1\\ \hfill 1& \hfill 1& \hfill 1& \hfill 1\\ \hfill 1& \hfill 1& \hfill 1& \hfill 1\\ \hfill 1& \hfill 1& \hfill 1& \hfill 1\end{array}\right].$$
(74)
The state with non-vanishing eigenvalue is again the $`A_1`$ eigenstate. After a little bit of algebra we have shown that under $`T_l`$ the subspace of $`A_1`$ and $`B_2`$ symmetry is exchanged with the one of $`E_x`$ and $`E_y`$ symmetry. Thus we can build a 4-body eigenstate of $`W_{\mathrm{Hubbard}}`$ with vanishing eigenvalue: $`|\psi _{A_1}^{}\psi _{B_2}^{}_\sigma |\psi _{E_x}^{}\psi _{E_y}^{}_\sigma `$. As before under a lattice step translation this state does not change its spatial distribution but $`\sigma \sigma `$ without any phase factor: $`|\psi _{A_1}^{}\psi _{B_2}^{}_\sigma |\psi _{E_x}^{}\psi _{E_y}^{}_\sigma |\psi _{E_x}^{}\psi _{E_y}^{}_\sigma |\psi _{A_1}^{}\psi _{B_2}^{}_\sigma `$.

Now we use these results to diagonalize $`n_{𝐫=0}`$ on the whole set $`𝒮_{hf}`$ (we could have done that directly by diagonalizing $`6\times 6`$ matrices but we wanted to show the general method). The eigenstate of $`n_{𝐫=0}`$ with nonvanishing eigenvalue always belongs to $`A_1`$. The matrix $`n_𝐫`$ has eigenvalues $`3/8`$ and (5 times) $`0`$, as predicted by Eq.(71). For $`𝐫=0`$ the eigenvector of occupation $`3/8`$ is $`|\phi _1^{(0)}=\frac{1}{\sqrt{3}}|\psi _{A_1}^{\prime \prime }+\sqrt{\frac{2}{3}}|\psi _{A_1}^{}`$. The other $`A_1`$ eigenstate of $`n_{𝐫=0}`$ has 0 eigenvalue and reads: $`|\phi _2^{(0)}=\sqrt{\frac{2}{3}}|\psi _{A_1}^{\prime \prime }\frac{1}{\sqrt{3}}|\psi _{A_1}^{}`$. The other eigenvectors, whose symmetry differs from $`A_1`$, are $`|\phi _3^{(0)}=|\psi _{B_2}^{}`$, $`|\phi _4^{(0)}=|\psi _{B_1}^{\prime \prime }`$, $`|\phi _5^{(0)}=|\psi _{E_x}^{}`$ and $`|\phi _6^{(0)}=|\psi _{E_y}^{}`$. One finds that the transfer matrices $`T_l`$ of Eq.(73) such that $`|\phi _I^{(\widehat{e}_l)}_J|\phi _J^{(0)}T_{l_{JI}}`$, are:

$$T_x=\left[\begin{array}{cccccc}\hfill 0& \hfill 0& \hfill 0& \hfill \frac{1}{\sqrt{3}}& \hfill i\sqrt{\frac{2}{3}}& \hfill 0\\ \hfill 0& \hfill 0& \hfill 0& \hfill \sqrt{\frac{2}{3}}& \hfill \frac{i}{\sqrt{3}}& \hfill 0\\ \hfill 0& \hfill 0& \hfill 0& \hfill 0& \hfill 0& \hfill i\\ \hfill \frac{1}{\sqrt{3}}& \hfill \sqrt{\frac{2}{3}}& \hfill 0& \hfill 0& \hfill 0& \hfill 0\\ \hfill i\sqrt{\frac{2}{3}}& \hfill \frac{i}{\sqrt{3}}& \hfill 0& \hfill 0& \hfill 0& \hfill 0\\ \hfill 0& \hfill 0& \hfill i& \hfill 0& \hfill 0& \hfill 0\end{array}\right],T_y=\left[\begin{array}{cccccc}\hfill 0& \hfill 0& \hfill 0& \hfill \frac{1}{\sqrt{3}}& \hfill 0& \hfill i\sqrt{\frac{2}{3}}\\ \hfill 0& \hfill 0& \hfill 0& \hfill \sqrt{\frac{2}{3}}& \hfill 0& \hfill \frac{i}{\sqrt{3}}\\ \hfill 0& \hfill 0& \hfill 0& \hfill 0& \hfill i& \hfill 0\\ \hfill \frac{1}{\sqrt{3}}& \hfill \sqrt{\frac{2}{3}}& \hfill 0& \hfill 0& \hfill 0& \hfill 0\\ \hfill 0& \hfill 0& \hfill i& \hfill 0& \hfill 0& \hfill 0\\ \hfill i\sqrt{\frac{2}{3}}& \hfill \frac{i}{\sqrt{3}}& \hfill 0& \hfill 0& \hfill 0& \hfill 0\end{array}\right].$$
(75)
The reason why this choice of the basis set is clever is now apparent. The local basis at any site $`r`$ splits into the subsets $`𝒮_a=\{|\phi _1^{(0)},|\phi _2^{(0)},|\phi _3^{(0)}\}`$, and $`𝒮_b=\{|\phi _4^{(0)},|\phi _5^{(0)},|\phi _6^{(0)}\}`$; a shift by a lattice step sends members of $`𝒮_a`$ into linear combinations of the members of $`𝒮_b`$, and conversely.

Consider the 6-body eigenstate of $`K`$

$$|\mathrm{\Phi }_{AF}_\sigma =|\phi _1^{(0)}\phi _2^{(0)}\phi _3^{(0)}_\sigma |\phi _4^{(0)}\phi _5^{(0)}\phi _6^{(0)}_\sigma .$$
(76)
In this state there is partial occupation of site $`𝐫=0`$ with spin $`\sigma `$, but no double occupation. It turns out that a shift by a lattice step produces the transformation

$$|\mathrm{\Phi }_{AF}_\sigma |\mathrm{\Phi }_{AF}_\sigma $$
(77)
that is, a lattice step is equivalent to a spin flip, a feature that we call antiferromagnetic property. Since the spin-flipped state is also free of double occupation, $`|\mathrm{\Phi }_{AF}_\sigma `$ is a $`W=0`$ eigenstate. A ground state which is a single determinant is a quite unusual property for an interacting model like this.

Note that $`|\phi _1^{(0)}\phi _2^{(0)}`$ is equivalent to $`|\psi _{A_1}^{\prime \prime }\psi _{A_1}^{}`$, because this is just a unitary transformation of the $`A_1`$ wave functions; so $`|\mathrm{\Phi }_{AF}_\sigma `$ can also be written in terms of the old local orbitals (without any mix of the local states of different irreps of $`𝐆`$):

$$|\mathrm{\Phi }_{AF}_\sigma =|\psi _{A_1}^{\prime \prime }\psi _{A_1}^{}\psi _{B_2}^{}_\sigma |\psi _{B_1}^{\prime \prime }\psi _{E_x}^{}\psi _{E_y}^{}_\sigma .$$
(78)
This form of the ground state lends itself to be generalised (see below). For $`N_\mathrm{\Lambda }>4`$, $`𝐤`$ vectors arise that do not possess any special symmetry, the vectors $`R_i𝐤`$ are all different for all $`R_iC_{4v}`$, and we get eight-dimensional irreps of $`𝐆`$. Recalling that $`|𝒮_{hf}|=2N_\mathrm{\Lambda }2`$, one finds that $`𝒮_{hf}`$ contains $`N_e=\frac{1}{2}(\frac{N_\mathrm{\Lambda }}{2}2)`$ irreps of dimension 8, one of dimension 4 and one of dimension 2 if $`N_\mathrm{\Lambda }/2`$ is even and $`N_o=\frac{1}{2}(\frac{N_\mathrm{\Lambda }}{2}1)`$ irreps of dimension 8 and one of dimension 2 if $`N_\mathrm{\Lambda }/2`$ is odd.

To extend the theory to general $`N_\mathrm{\Lambda }`$, we note that these $`𝐤`$ vectors, since $`R_i𝐤`$ are all different, are a basis of the regular representation of $`C_{4v}`$. Thus, by the Burnside theorem, each of them breaks into $`A_1A_2B_1B_2EE`$; diagonalizing $`n_{𝐫=0}`$ and the point group characters on the basis of the $`m`$-th eight-dimensional irrep of $`𝐆`$ one gets one-body states $`|\psi _I^{[m]}`$, where $`I`$ stands for the $`C_{4v}`$ irrep label, $`I`$=$`A_1`$, $`A_2`$, $`B_1`$, $`B_2`$, $`E_x`$, $`E_y`$, $`E_x^{}`$, $`E_y^{}`$; here we denote by $`E^{}`$ the second occourrence of the irrep $`E`$. The ground state wave function in $``$ for the half filled case is a generalized version of Eq.(78). For even $`N_\mathrm{\Lambda }/2`$, we have

$$|\mathrm{\Phi }_{AF}_\sigma |(\underset{m=1}{\overset{N_e}{}}\psi _{A_1}^{[m]}\psi _{B_2}^{[m]}\psi _{E_x}^{[m]}\psi _{E_y}^{[m]})\psi _{A_1}^{}\psi _{B_2}^{}\psi _{A_1}^{\prime \prime }_\sigma |(\underset{m=1}{\overset{N_e}{}}\psi _{A_2}^{[m]}\psi _{B_1}^{[m]}\psi _{E_x^{}}^{[m]}\psi _{E_y^{}}^{[m]})\psi _{E_x}^{}\psi _{E_y}^{}\psi _{B_1}^{\prime \prime }_\sigma ,$$
(79)
with $`\sigma =,`$. For odd $`N_\mathrm{\Lambda }/2`$, $`|\mathrm{\Phi }_{AF}_\sigma `$ is similar but the maximum $`m`$ is $`N_o`$ and the $`|\psi ^{}`$ states do not occour. $`|\mathrm{\Phi }_{AF}_\sigma `$ is a $`W=0`$ state, transforms into $`|\mathrm{\Phi }_{AF}_\sigma `$ for each lattice step translation and manifestly shows an antiferromagnetic order (antiferromagnetic property). Since $`W_{\mathrm{H}ubbard}`$ is a positive semidefinite operator $`|\mathrm{\Phi }_{AF}_\sigma `$ is actually a ground state. In the basis of local states these are the only two determinantal states ($`\sigma =,`$) with the above properties.

A few further remarks about $`|\mathrm{\Phi }_{AF}_\sigma `$ are in order. (1) Introducing the projection operator $`P_S`$ on the spin $`S`$ subspace, one finds that $`P_S|\mathrm{\Phi }_{AF}_\sigma |\mathrm{\Phi }_{AF}^S_\sigma 0,S=0,\mathrm{},N_\mathrm{\Lambda }1`$. Then, $`{}_{\sigma }{}^{}\mathrm{\Phi }_{AF}|W_{\mathrm{H}ubbard}|\mathrm{\Phi }_{AF}_{\sigma }^{}=_{S=1}^{N_\mathrm{\Lambda }1}{}_{\sigma }{}^{}\mathrm{\Phi }_{AF}^S|W_{\mathrm{H}ubbard}|\mathrm{\Phi }_{AF}^S_{\sigma }^{}=0`$, and this implies that there is at least one ground state of $`W_{\mathrm{H}ubbard}`$ in $``$ for each $`S`$. The actual ground state of $`H_{\mathrm{H}ubbard}`$ at weak coupling is the singlet $`|\mathrm{\Phi }_{AF}^0_\sigma `$. (2) The existence of this singlet $`W=0`$ ground state is a direct consequence of the Lieb theorem. Indeed the maximum spin state $`|\mathrm{\Phi }_{AF}^{N_\mathrm{\Lambda }1}_\sigma `$ is trivially in the kernel of $`W_{\mathrm{H}ubbard}`$; since the ground state must be a singlet it should be an eigenvector of $`W_{\mathrm{H}ubbard}`$ with vanishing eigenvalue. (3) The above results and Lieb’s theorem imply that higher order effects split the ground state multiplet of $`H_{\mathrm{H}ubbard}`$ and the singlet is lowest. 4) The Lieb theorem makes no assumptions concerning the lattice structure; adding the ingredient of the $`𝐆`$ symmetry we are able to explicitly display the wave function at weak coupling.

Using the explicit form of $`P_{S=0}`$ one finds that $`P_{S=0}|\mathrm{\Phi }_{AF}_\sigma =P_{S=0}|\mathrm{\Phi }_{AF}_\sigma `$. This identity allows us to study how the singlet component transforms under translations, reflections and rotations. In particular the antiferromagnetic property tells us that the total momentum is $`K_{tot}=(0,0)`$. To make contact with Ref. we have also determined how it transforms under the $`C_{4v}`$ operations with respect to the center of an arbitrary placquette. It turns out that it is even under reflections and transforms as an $`s`$ wave if $`N_\mathrm{\Lambda }/2`$ is even and as a $`d`$ wave if $`N_\mathrm{\Lambda }/2`$ is odd.

In the next Section we use these results, togheter with the non-perturbative canonical transformation, to study the doped $`4\times 4`$ lattice at half filling. Since the non-interacting ground state at half filling is now well known and unambiguously defined the expansion (48) can be performed in a unique way.

### F Pairing in the Doped Hubbard Antiferromagnet

Let us represent the $`4\times 4`$ lattice as in Figure 9 (A).

We consider a 4$`\times `$4 lattice one-band Hubbard Model and periodic boundary conditions. The one particle energy spectrum of the kinetic term $`K`$ has 5 equally spaced levels having degeneracy 1, 4, 6, 4, 1 respectively. The space Group $`𝐆`$ containing the translations and the 8 $`C_{4v}`$ operations is not enough to explain the degeneracy 6. Indeed the largest dimension of the irreps of the space Group for this 4$`\times `$4 lattice is 4. Nevertheless the 4$`\times `$4 lattice is very special, since among the symmetry operations that preserve $`K`$ there are some which are not contained in $`𝐆`$ and preserve $`W_{\mathrm{Hubbard}}`$ too. This fact implies that $`H_{\mathrm{Hubbard}}`$ is invariant under a new and largest symmetry Group; let us call it $`𝒢`$. As observed by previous authors the 4$`\times `$4 lattice can be mapped in the $`2\times 2\times 2\times 2`$ hypercube since each pair of next to nearest neighbor sites has two nearest neighbor sites in common. Due to the importance of the symmetry in our configuration interaction mechanism, below we explicitly build a new symmetry operations and derive the character table of $`𝒢`$.

#### 1 Symmetry Group of the $`4\times 4`$ lattice

Periodic boundary conditions are assumed and for example, the nearest neighbours of 1 are 2, 5, 4 and 13. Rotating the plaquettes 1, 2, 5, 6 and 11 ,12 ,15, 16 clockwise and the other two counterclockwise by 90 degrees we obtain the effect of the dynamical symmetry, that we call $`d`$, see Figure 9 (B). This transformation preserves nearest neighbours (and so, each order of neighbours) but is not an isometry, and for example the distance between 1 and 3 changes. Thus, this symmetry operation $`d`$ is a new, dynamical symmetry. Including $`d`$ and closing the multiplication table we obtain the Group $`𝒢`$ with 384 elements in 20 classes (like $`𝐆`$). The complete Character Table of $`𝒢`$ is shown in the Table X.

As the notation suggests, the irreps $`A_1`$ and $`\stackrel{~}{A}_1`$ both reduce to $`A_1`$, in $`C_{4v}`$, while $`B_2`$ and $`\stackrel{~}{B}_2`$ both reduce to $`B_2`$. In the Table XI we report the one-body eigenvalues of for $`t=1`$, the degeneracy and the symmetry of each eigenvector. For pairs, the $`W=0`$ theorem of Section II A 2 ensures that no double occupancy is possible in the irreps $`\stackrel{~}{A}_1,B_2,\mathrm{\Gamma }_1,\mathrm{\Gamma }_2,\mathrm{\Sigma }_1,\mathrm{\Sigma }_2,\mathrm{\Sigma }_3,\mathrm{\Sigma }_4,\mathrm{\Lambda }_2,\mathrm{\Lambda }_3,\mathrm{\Omega }_1,\mathrm{\Omega }_2,\mathrm{\Omega }_3,\mathrm{\Pi }_1`$ and $`\mathrm{\Pi }_2`$ not represented in the one-body spectrum.

The exact interacting ground state of the system with 4 holes is threefold degenerate and belongs to an irrep of $`𝒢`$ that contains the irreps $`A_1`$ and $`B_1`$ of $`C_{4v}`$ once and two times respectively. This irrep is not contained in the one particle spectrum of $`K`$, which does not admit degeneracy 3. By the $`W=0`$ theorem, pairs belonging to it must be $`W=0`$ pairs. These $`W=0`$ pairs arise from the single-particle states of $`K`$ with eigenvalue -2, and their irrep is contained in the square of the irrep of the single-particle level.

The $`m`$ states of the expansion (48) are all the $`W=0`$ pairs belonging to the ground state irrep. The binding energy $`|\mathrm{\Delta }(4)|`$ can be computed analitically by truncating the configuration interaction expansion (48) to the $`\alpha `$ states and also by means of exact diagonalization. The results are listed below for different values of the on-site interaction $`U`$ (energies are in eV):

|  | $`U=`$0.1 | $`U=`$0.5 | $`U=`$0.7 | $`U=`$1 |
| --- | --- | --- | --- | --- |
| $`\mathrm{\Delta }(4)_{\mathrm{exact}}`$ | -0.053 | -0.32 | -0.67 | -1.18 |
| $`\mathrm{\Delta }(4)_{\mathrm{analytic}}`$ | -0.078 | -1.95 | -3.83 | -7.81 |

As expected, with increasing $`U`$ the difference $`|\mathrm{\Delta }(4)_{\mathrm{exact}}\mathrm{\Delta }(4)_{\mathrm{analytic}}|`$ increases because the renormalization induced by virtual electron-hole exitations becomes important and it is no longer a good approximation to consider the $`\alpha `$ states only. Nevertheless the truncated canonical transformation still predicts the right sign of $`\mathrm{\Delta }`$.

As observed in Section III E the above canonical transformation applies when two holes are added to a non-degenerate vacuum. To study the system at and close to half filling, we have to use the results of Section III E. In the following we will solve the problem of two electrons added to the half filled system.

#### 2 $`W=0`$ Pairs and Quartets

Here we use the antiferromagnetic ground state $`|\mathrm{\Phi }_{AF}^{S=0}`$ to predict the possible symmetries of the doped half filled system. With 12 holes, in the $`U0`$ limit, there are two in $`𝒮_{hf}`$; the first-order ground states correspond to $`W=0`$ pairs. The symmetry of these $`W=0`$ states can be determined a priori from the $`𝒢`$ irreps of Table XI. Apart from the filled shells, two holes go to the $`\mathrm{\Omega }_4`$ level. From the character of $`𝒢`$ one can derive that

$$\mathrm{\Omega }_4^2=A_1+\stackrel{~}{B}_2+\mathrm{\Omega }_4+\mathrm{\Gamma }_1+\mathrm{\Gamma }_2+\mathrm{\Sigma }_2+\mathrm{\Sigma }_3+\mathrm{\Omega }_1+\mathrm{\Omega }_2+\mathrm{\Omega }_3;$$
(80)
since the first 3 entries are present in Table XI, the $`W=0`$ theorem ensures that $`\mathrm{\Gamma }_1`$, $`\mathrm{\Gamma }_2`$, $`\mathrm{\Sigma }_2`$, $`\mathrm{\Sigma }_3`$, $`\mathrm{\Omega }_1`$, $`\mathrm{\Omega }_2`$ and $`\mathrm{\Omega }_3`$ pairs have no double occupation. It turns out that the spin and orbital symmetries are entangled, i.e. some of these pairs are triplet and the rest singlet. We can see that by projecting the determinantal state $`c_𝐤^{}c_𝐩^{}|0`$ with $`𝐤,𝐩𝒮_{hf}`$ on the irreps not contained in the spectrum. One obtaines singlet $`W=0`$ pairs for $`\mathrm{\Gamma }_1,\mathrm{\Gamma }_2,\mathrm{\Sigma }_2,\mathrm{\Omega }_1`$. Other irreps yield $`W=0`$ triplet pairs. They are the three times degenerate irrep $`\mathrm{\Sigma }_3`$ and the two sixfold set of $`\mathrm{\Omega }_2`$ and $`\mathrm{\Omega }_3`$ symmetry. The above a priori argument hardly applies to the symmetries of $`W=0`$ quartets, because $`\mathrm{\Omega }_4^4`$ contains almost every symmetry and we do not know any $`W=0`$-like theorem for quartets. However, we can still build the projection operators by Mathematica; we can project the 225 quartets on the irreps of $`𝒢`$ and carry on the analysis in an efficient, if not elegant, way. It was found that the singlet $`W=0`$ quartets are 13 as many as the singlet $`W=0`$ pairs, and belong to the same irreps $`\mathrm{\Gamma }_1,\mathrm{\Gamma }_2,\mathrm{\Sigma }_2,\mathrm{\Omega }_1`$. Therefore, these are the possible symmetries of the first-order ground states with 14 holes. Exact diagonalization results show that for $`U/t<3`$ and $`162=14`$ holes the ground state is sixfold degenerate, with a doublet of states with momentum $`(\pi ,\pi )`$ and a quartet with momentum $`(\pm \pi /2,\pm \pi /2)`$. It can be shown that the computed ground state corresponds to an $`\mathrm{\Omega }_1`$ electron pair over the half filled system. For $`U/t>3`$ and the same number of holes a level crossing takes place: the ground state is threefold degenerate and contains a state with momentum $`(0,0)`$ and a doublet with momentum $`(\pi ,0)`$ and $`(0,\pi )`$. The computed ground state must be assigned to a $`\mathrm{\Sigma }_2`$ electron pair over the half filled system. In both cases, the symmetry of the ground state corresponds to a $`W=0`$ pair.

#### 3 Pairing mechanism

We consider the ground state of the $`4\times 4`$ model with 14 holes; aside from the 10 holes in the inner $`A_1`$ and $`\mathrm{\Lambda }_1`$ shells (see Table XI) the outer $`\mathrm{\Omega }_4`$ shell contains 4 holes in a $`W=0`$ quartet. We are in position to show that pairing between two electrons added to the antiferromagnetic 16-holes ground state (half filling) comes out.

We recall from Section III F 2 that, by comparing with exact diagonalization results, the ground state is assigned to $`\mathrm{\Omega }_1`$ at weak coupling and to $`\mathrm{\Sigma }_2`$ at a stronger coupling. We must preliminarily verify that Group Theory does not forbid obtaining these symmetries by creating $`W=0`$ electron pairs from the antiferromagnetic state $`|\mathrm{\Phi }_{AF}^{S=0}`$. This is the same as annihilating hole pairs. Since the state $`|\mathrm{\Phi }_{AF}^{S=0}`$ is a total symmetric singlet with vanishing total momentum, the labels of the quartets will be the same of the annihilated hole pairs. This operation can be done by hand, or with the help of Mathematica, and the answer to the preliminary question is adfirmative for $`\mathrm{\Omega }_1`$ and $`\mathrm{\Sigma }_2`$, but not for all pairs. One obtains 24 $`W=0`$ quartets out of the 28 states since the annihilation of $`\mathrm{\Gamma }_1`$ and $`\mathrm{\Gamma }_2`$ $`W=0`$ pairs gives identically zero.

Next, we have to use the antiferromagnetic ground state $`|\mathrm{\Phi }_{AF}^{S=0}`$ as the non-interacting ground state of the configuration interaction expansion (48). In small clusters like the $`4\times 4`$ one the one-body states are widely separated and the intra-shell interaction is much more important than the inter-shell one; therefore, we consider only the $`m`$ states made removing two holes in $`𝒮_{hf}`$ from $`|\mathrm{\Phi }_{AF}^{S=0}`$, neglecting the high-lying unoccupied orbitals. The explicit calculations shown that the effective interaction is attractive for both $`\mathrm{\Omega }_1`$ and $`\mathrm{\Sigma }_2`$ $`W=0`$ pairs leading to a bound state with binding energy $`\mathrm{\Delta }_{\mathrm{\Omega }_1}=61.9`$ meV and $`\mathrm{\Delta }_{\mathrm{\Sigma }_2}=60.7`$ meV for $`U=t=1`$ eV. Therefore, the true weak coupling ground state is a $`\mathrm{\Omega }_1`$ $`W=0`$ pair over the antiferromagnetic state. This result agree with exact diagonalization data.

## IV Conclusions

We have presented the following evidence that the $`W=0`$ pairs are the quasi-particles that, once dressed, play the rôle of Cooper pairs: 1) as two-body states they do not feel the large on-site repulsion, that would come in first-order perturbation in any theory of pairing with any other kind of pairs. 2) The indirect interaction with the background particles gives attraction, and bound states with physically appealing binding energies. 3) The same results are also borne out by exact diagonalisation in finite clusters, if and only if they have the correct symmetry and filling to give raise to $`W=0`$ pairs. 4) Both in clusters and in the plane, superconducting flux quantisation results from the symmetry properties of $`W=0`$ pairs.

The setup of our theory of the effective interaction $`W_{\mathrm{e}ff}`$ between two holes (or electrons) is quite general; although we developed it in detail for Hubbard Models, we can readily include phonons and other ingredients. In principle we can obtain $`W_{\mathrm{e}ff}`$ by our canonical transformation, including systematically any kind of virtual intermediate states. The closed-form analytic expression of $`W_{\mathrm{e}ff}`$ we obtained includes 4-body virtual states. This describes repeated exchange of an electron-hole pair to all orders. One can envisage the pairing mechanism by spin-flip exchange diagrams that are enhanced by the $`C_{4v}`$ symmetry. The argument does not depend in any way on perturbation theory, and the equations retain their form, with renormalized parameters, at all orders. The previous exact-diagonalisation results of cluster calculations are special cases. The resulting integral equation (66), with the effective interaction (65), is valid for the full plane. Since an analytic treatment is prohibitive, we resort to a numerical treatment. We find that in the three-band Hubbard Model, $`{}_{}{}^{1}A_{2}^{}`$ pairs are more tightly bound close to half filling, but $`{}_{}{}^{1}B_{2}^{}`$ pairs are favored when the filling increases. We remind here that these symmetry labels are not absolute, but depend on the choice of a gauge convention. We get attraction and pairing at all fillings we have considered (above half filling), but the binding energy of the $`{}_{}{}^{1}A_{2}^{}`$ pairs drops by orders of magnitude as the filling increases; thus, there is no chance of superconducting flux quantization too far from half filling. So, we do not predict that superconductivity occurs outside some range of hole concentration. However, pairing is still there, even for large doping. The three-band Hubbard Model might be too idealized to allow a detailed comparison with experiments; however we stress that the approach presented is far more general than the model we are using, and can be applied to more realistic Hamiltonians.

The above non-perturbative canonical transformation allows to study pairing fluctuations when the non-interacting ground state is unique (non-degenerate). Nevertheless, at exactly half filling, the ground state is highly degenerate and the configuration interaction expansion of Section III C is not well defined any more. To overcome the problem, we have removed the degeneracy in first order and with the help of the Lieb’s theorem we have found the exact ground state of the half filled one-band Hubbard Model at weak coupling. We have shown that its symmetry quantum numbers are the same as in the strong coupling case. This result was estabilished for square lattices of arbitrary size.

Once the degeneracy is removed the non-perturbative canonical transformation can be applied and the interesting question of what happens by doping the Hubbard antiferromagnet can be explored analytically. Therefore, we test the $`W=0`$ pairing mechanism within the one-band Hubbard Model with periodic boundary conditions using exact numerical data on the $`4\times 4`$ square lattice. In particular, several workers have recognised that those data could be qualitatively understood by a weak coupling analysis; however the evidence of pairing was not seen and the symmetry analysis of the system was not complete. Furthermore, the role of $`W=0`$ states had not been discovered and the reason of the apparent success of the weak coupling analysis was not clarified. In our approach, the criteria exploited in the fully symmetric clusters of the CuO2 plane are used to unambiguosly diagnose pairing. One more time the effective attractive interaction comes out from a spin flip diagram. This result lends further support to the general approach which predicts the existence of pairing fluctuations for systems of arbitrary size.

On the other hand, the above results also prove that important ingredients are still missing and must be included. The $`4\times 4`$ model shows evidence of bound pairs of non-vanishing momentum, in degenerate representations. This opens up the possibility of charge inhomogeneities and Jahn-Teller distorsions, that remain to be explored.

REFERENCES