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# Topological Quantum Field Theory for Calabi-Yau threefolds and 𝐺₂-manifolds

## 1 Introduction

In the past two decades we have witnessed many fruitful interactions between mathematics and physics. One example is in the Donaldson-Floer theory for oriented four manifolds. Physical considerations lead to the discovery of the Seiberg-Witten theory which has profound impact to our understandings of four manifolds. Another example is in the mirror symmetry for Calabi-Yau manifolds. This duality transformation in the string theory leads to many surprising predictions in the enumerative geometry.

String theory in physics studies a ten dimensional space-time $`X\times ^{3,1}`$. Here $`X`$ a six dimensional Riemannian manifold with its holonomy group inside $`SU\left(3\right)`$, the so-called Calabi-Yau threefold. Certain parts of the mirror symmetry conjecture, as studied by Vafa’s group, are specific for Calabi-Yau manifolds of complex dimension three. They include the Gopakumar-Vafa conjecture for the Gromov-Witten invariants of arbitrary genus, the Ooguri-Vafa conjecture on the relationships between knot invariants and enumerations of holomorphic disks and so on. The key reason is they belong to a duality theory for $`G_2`$-manifolds. $`G_2`$-manifolds can be naturally interpreted as special Octonion manifolds . For any Calabi-Yau threefold $`X`$, the seven dimensional manifold $`X\times S^1`$ is automatically a $`G_2`$-manifold because of the natural inclusion $`SU\left(3\right)G_2`$.

In recent years, there are many studies of $`G_2`$-manifolds in M-theory including works of Archaya, Atiyah, Gukov, Vafa, Witten, Yau, Zaslow and many others (e.g. , , , ).

In the studies of the symplectic geometry of a Calabi-Yau threefold $`X`$, we consider unitary flat bundles over three dimensional (special) Lagrangian submanifolds $`L`$ in $`X`$. The corresponding geometry for a $`G_2`$-manifold $`M`$ is called the special $``$-Lagrangian geometry (or C-geometry in ). where we consider Anti-Self-Dual (abbrev. ASD) bundles over four dimensional coassociative submanifolds, or equivalently special $``$-Lagrangian submanifolds of type II ,  (abbrev. $``$-SLag) $`C`$ in $`M`$.

Counting ASD bundles over a fixed four manifold $`C`$ is the well-known theory of Donaldson differentiable invariants, $`Don\left(C\right)`$. Similarly, counting unitary flat bundles over a fixed three manifold $`L`$ is Floer’s Chern-Simons homology theory, $`HF_{CS}\left(L\right)`$. When $`C`$ is a connected sum $`C_1\mathrm{\#}_LC_2`$ along a homology three sphere, the relative Donaldson invariants $`Don\left(C_i\right)`$’s take values in $`HF_{CS}\left(L\right)`$ and $`Don\left(C\right)`$ can be recovered from individual pieces by a gluing theorem, $`Don\left(C\right)=Don\left(C_1\right),Don\left(C_2\right)_{HF_{CS}\left(L\right)}`$ (see e.g. ). Similarly when $`L`$ has a handlebody decomposition $`L=L_1\mathrm{\#}_\mathrm{\Sigma }L_2`$, each $`L_i`$ determines a Lagrangian subspace $`_i`$ in the moduli space $`^{flat}\left(\mathrm{\Sigma }\right)`$ of unitary flat bundles over the Riemann surface $`\mathrm{\Sigma }`$ and Atiyah conjectures that we can recover $`HF_{CS}\left(L\right)`$ from the Floer’s Lagrangian intersection homology group of $`_1`$ and $`_2`$ in $`^{flat}\left(\mathrm{\Sigma }\right)`$, $`HF_{CS}\left(L\right)=HF_{Lag}^{^{flat}\left(\mathrm{\Sigma }\right)}(_1,_2)`$. Such algebraic structures in the Donaldson-Floer theory can be formulated as a Topological Quantum Field Theory (abbrev. TQFT), as defined by Segal and Atiyah .

In this paper, we propose a construction of a TQFT by counting ASD bundles over four dimensional $``$-SLag $`C`$ in any closed (almost) $`G_2`$-manifold $`M`$. We call these $``$-SLag cycles and they can be identified as zeros of a naturally defined closed one form on the configuration space of topological cycles. We expect to obtain a homology theory $`H_C\left(M\right)`$ by applying the construction in the Witten’s Morse theory. When $`M`$ is non-compact with an asymptotically cylindrical end, $`X\times [0,\mathrm{})`$, then the collection of boundary data of relative $``$-SLag cycles determines a Lagrangian submanifold $`_M`$ in the moduli space $`^{SLag}\left(X\right)`$ of special Lagrangian cycles in the Calabi-Yau threefold $`X`$.

When we decompose $`M=M_1\mathrm{\#}_XM_2`$ along an infinite asymptotically cylindrical neck, it is reasonable to expect to have a gluing formula,

$$H_C\left(M\right)=HF_{Lag}^{^{SLag}\left(X\right)}(_{M_1},_{M_2})\text{.}$$

The main technical difficulty in defining this TQFT rigorously is the compactness issue for the moduli space of $``$-SLag cycles in $`M`$. We do not know how to resolve this problem and our homology groups are only defined in the formal sense (and physical sense?).

## 2 $`G_2`$-manifolds and $``$-SLag geometry

We first review some basic definitions and properties of $`G_2`$-geometry, see  for more details.

###### Definition 1.

A seven dimensional Riemannian manifold $`M`$ is called a $`G_2`$-manifold if the holonomy group of its Levi-Civita connection is inside $`G_2SO\left(7\right)`$.

The simple Lie group $`G_2`$ can be identified as the subgroup of $`SO\left(7\right)`$ consisting of isomorphism $`g:^7^7`$ preserving the linear three form $`\mathrm{\Omega }`$,

$$\mathrm{\Omega }=f^1f^2f^3f^1\left(e^1e^0+e^2e^3\right)f^2\left(e^2e^0+e^3e^1\right)f^3\left(e^3e^0+e^1e^2\right)\text{,}$$

where $`e^0,e^1,e^2,e^3,f^1,f^2,f^3`$ is any given orthonormal frame of $`^7`$. Such a three form, or up to conjugation by elements in $`GL(7,)`$, is called positive, and it determines a unique compatible inner product on $`^7`$ .

Gray  shows that $`G_2`$-holonomy of $`M`$ can be characterized by the existence of a positive harmonic three form $`\mathrm{\Omega }`$.

###### Definition 2.

A seven dimensional manifold $`M`$ equipped with a positive closed three form $`\mathrm{\Omega }`$ is called an almost $`G_2`$-manifold.

Remark: The relationship between $`G_2`$-manifolds and almost $`G_2`$-manifolds is analogous to the relationship between Kahler manifolds and symplectic manifolds. Namely we replace a parallel non-degenerate form by a closed one.

For example, suppose that $`X`$ is a complex three dimensional Kähler manifold with a trivial canonical line bundle, i.e. there exists a nonvanishing holomorphic three form $`\mathrm{\Omega }_X`$. Yau’s celebrated theorem says that there is a Kähler form $`\omega _X`$ on $`X`$ such that the corresponding Kahler metric has holonomy in $`SU\left(3\right)`$, i.e. a Calabi-Yau threefold. In particular both $`\mathrm{\Omega }_X`$ and $`\omega _X`$ are parallel forms. Then the product $`M=X\times S^1`$ is a $`G_2`$-manifold with

$$\mathrm{\Omega }=\mathrm{Re}\mathrm{\Omega }_X+\omega _Xd\theta \text{.}$$

Conversely, one can prove, using Bochner arguments, every $`G_2`$-metric on $`X\times S^1`$ must be of this form. More generally, if $`\omega _X`$ is a general Kähler form on $`X`$, then $`(X\times S^1,\mathrm{\Omega })`$ is an almost $`G_2`$-manifold and the converse is also true.

Next we quickly review the geometry of $``$-SLag cycles in an almost $`G_2`$-manifold (see ).

###### Definition 3.

An orientable four dimensional submanifold $`C`$ in an almost $`G_2`$-manifold $`(M,\mathrm{\Omega })`$ is called a coassociative submanifold, or simply a $``$-SLag, if the restriction of $`\mathrm{\Omega }`$ to $`C`$ is identically zero,

$$\mathrm{\Omega }|_C=0\text{.}$$

If $`M`$ is a $`G_2`$-manifold, then any coassociative submanifold $`C`$ in $`M`$ is calibrated by $`\mathrm{\Omega }`$ in the sense of Harvey and Lawson , in particular, it is an absolute minimal submanifold in $`M`$. The normal bundle of any $``$-SLag $`C`$ can be naturally identified with the bundle of self-dual two forms on $`C`$. McLean  shows that infinitesimal deformations of any $``$-SLag are unobstructed and they are parametrized by the space of harmonic self-dual two forms on $`C`$, i.e. $`H_+^2(C,)`$.

For example, if $`S`$ is a complex surface in a Calabi-Yau threefold $`X`$, then $`S\times \left\{t\right\}`$ is a $``$-SLag in $`M=X\times S^1`$ for any $`tS^1`$. Notice that $`H_+^2(S,)`$ is spanned by the Kahler form and the real and imaginary parts of holomorphic two forms on $`S`$, and the latter can be identified holomorphic normal vector fields along $`S`$ because of the adjunction formula and the Calabi-Yau condition on $`X`$. Thus all deformations of $`S\times \left\{t\right\}`$ in $`M`$ as $``$-SLag submanifolds are of the same form. Similarly, if $`L`$ is a three dimensional special Lagrangian submanifold in $`X`$ with phase $`\pi /2`$, i.e. $`\omega |_L=\mathrm{Re}\mathrm{\Omega }_X|_L=0`$, then $`L\times S^1`$ is also a $``$-SLag in $`M=X\times S^1`$. Furthermore, all deformations of $`L\times S^1`$ in $`M`$ as $``$-SLag submanifolds are of the same form because $`H_+^2\left(L\times S^1\right)H^1\left(L\right)`$, which parametrizes infinitesimal deformations of special Lagrangian submanifolds in $`X`$.

###### Definition 4.

A $``$-SLag cycle in an almost $`G_2`$-manifold $`(M,\mathrm{\Omega })`$ is a pair $`(C,D_E)`$ with $`C`$ a $``$-SLag in $`M`$ and $`D_E`$ an ASD connection over $`C`$.

Remark: $``$-SLag cycles are supersymmetric cycles in physics as studied in . Their moduli space admits a natural three form and a cubic tensor , which play the roles of the correlation function and the Yukawa coupling in physics.

We assume that the ASD connection $`D_E`$ over $`C`$ has rank one, i.e. a $`U\left(1\right)`$ connection. This avoids the occurrence of reducible connections, thus the moduli space $`^{SLag}\left(M\right)`$ of $``$-SLag cycles in $`M`$ is a smooth manifold. It has a natural orientation and its expected dimension equals $`b^1\left(C\right)`$, the first Betti number of $`C`$. This is because the moduli space of $``$-SLags has dimension equals $`b_+^2\left(C\right)`$  and the existence of an ASD $`U\left(1\right)`$-connection over $`C`$ is equivalent to $`H_{}^2(C,)H^2(C,)\varphi `$. The number $`b^1\left(C\right)`$ is responsible for twisting by a flat $`U\left(1\right)`$-connection.

For simplicity, we assume that $`b^1\left(C\right)=0`$, otherwise, one can cut down the dimension of $`^{SLag}\left(M\right)`$ to zero by requiring the ASD connections over $`C`$ to have trivial holonomy around loops $`\gamma _1,\mathrm{},\gamma _{b^1\left(C\right)}`$ in $`C`$ representing an integral basis of $`H_1(C,)`$. We plan to count the algebraic number of points in this moduli space $`\mathrm{\#}^{SLag}\left(M\right)`$.

This number, in the case of $`X\times S^1`$, can be identified with a proposed invariant of Joyce  defined by counting rigid special Lagrangian submanifolds in any Calabi-Yau threefold. To explain this, we need the following proposition on the strong rigidity of product $``$-SLags.

###### Proposition 5.

If $`L\times S^1`$ is a $``$-SLag in $`M=X\times S^1`$ with $`X`$ a Calabi-Yau threefold, then any $``$-SLag representing the same homology class must also be a product.

Proof: For simplicity we assume that the volume of the $`S^1`$ factor is unity, $`Vol\left(S^1\right)=1`$. If $`L\times S^1`$ is a $``$-SLag in $`M`$ then $`L`$ is special Lagrangian submanifold in $`X`$ with phase $`\pi /2`$, i.e. $`\mathrm{Re}\mathrm{\Omega }_X|_L=\omega |_L=0`$. Suppose $`C`$ is another $``$-SLag in $`M`$ representing the same homology class, we have $`Vol\left(C\right)=Vol\left(L\right)`$. If we write $`C_\theta =C\left(X\times \left\{\theta \right\}\right)`$ for any $`\theta S^1`$, then $`Vol\left(C_\theta \right)Vol\left(L\right),`$ as $`L`$ is a calibrated submanifold in $`X`$. Furthermore the equality sign holds only if $`C_\theta `$ is also calibrated. In general we have

$$Vol\left(C\right)_{S^1}Vol\left(C_\theta \right)𝑑\theta ,$$

with the equality sign holds if and only if $`C`$ is a product with $`S^1`$. Combining these, we have

$$Vol\left(L\right)=Vol\left(C\right)_{S^1}Vol\left(C_\theta \right)𝑑\theta _{S^1}Vol\left(L\right)𝑑\theta =Vol\left(L\right)\text{.}$$

Thus both inequalities are indeed equal. Hence $`C=L^{}\times S^1`$ for some special Lagrangian submanifold $`L^{}`$ in $`X`$. $`\mathrm{}`$

Suppose $`M=X\times S^1`$ is a product $`G_2`$-manifold and we consider product $``$-SLag $`C=L\times S^1`$ in $`M`$. From the above proposition, every $``$-SLag representing $`\left[C\right]`$ must also be a product. Since $`b_+^2\left(C\right)=b^1\left(L\right)`$, the rigidity of the $``$-SLag $`C`$ in $`M`$ is equivalent to the rigidity of the special Lagrangian submanifold $`L`$ in $`X`$. When this happens, i.e. $`L`$ is a rational homology three sphere, we have $`b^2\left(C\right)=0`$ and

$$\text{No. of ASD U(1)-bdl/}C=\mathrm{\#}H^2(C,)=\mathrm{\#}H^2(L,)=\mathrm{\#}H_1(L,)\text{.}$$

Here we have used the fact that the first cohomology group is always torsion free. Thus the number of such $``$-SLag cycles in $`X\times S^1`$ equals the number of special Lagrangian rational homology three spheres in a Calabi-Yau threefold $`X`$, weighted by $`\mathrm{\#}H_1(L,)`$. Joyce  shows that with this particular weight, the numbers of special Lagrangians in any Calabi-Yau threefold behave well under various surgeries on $`X`$, and expects them to be invariants. Thus in this case, we have

$$\mathrm{\#}^{SLag}\left(X\times S^1\right)=\text{Joyce’s proposed invariant for }\mathrm{\#}\text{SLag. in }X\text{.}$$

In the next section, we will propose a homology theory, whose Euler characteristic gives $`\mathrm{\#}^{SLag}\left(M\right)`$.

## 3 Witten’s Morse theory for $``$-SLag cycles

We are going to use the parametrized version of $``$-SLag cycles in any almost $`G_2`$-manifold $`M`$. We fix an oriented smooth four dimensional manifold $`C`$ and a rank $`r`$ Hermitian vector bundle $`E`$ over $`C`$. We consider the configuration space

$$𝒞=Map(C,M)\times 𝒜\left(E\right),$$

where $`𝒜\left(E\right)`$ is the space of Hermitian connections on $`E`$.

###### Definition 6.

An element $`(f,D_E)`$ in $`𝒞`$ is called a parametrized $``$-SLag cycles in $`M`$ if

$$f^{}\mathrm{\Omega }=F_E^+=0\text{,}$$

where the self-duality is defined using the pullback metric from $`M`$.

Instead of $`Aut\left(E\right)`$, the symmetry group $`𝒢`$ in our situation consists of gauge transformations of $`E`$ which cover arbitrary diffeomorphisms on $`M`$,

$$\begin{array}{ccc}E& \stackrel{𝑔}{}& E\\ & & \\ M& \stackrel{g_M}{}& M.\end{array}$$

It fits into the following exact sequence,

$$1Aut\left(E\right)𝒢Diff\left(C\right)1\text{.}$$

The natural action of $`𝒢`$ on $`𝒞`$ is given by

$$g(f,D_E)=(fg_M,g^{}D_E),$$

for any $`(f,D_E)𝒞=Map(C,M)\times 𝒜\left(E\right)`$. Notice that $`𝒢`$ preserves the set of parametrized $``$-SLag cycles in $`M`$.

The configuration space $`𝒞`$ has a natural one form $`\mathrm{\Phi }_0`$: At any $`(f,D_E)𝒞`$ we can identify the tangent space of $`𝒞`$ as

$$T_{(f,D_E)}𝒞=\mathrm{\Gamma }(C,f^{}T_M)\times \mathrm{\Omega }^1(C,ad\left(E\right))\text{.}$$

We define

$$\mathrm{\Phi }_0(f,D_E)(v,B)=_CTr\left[f^{}\left(\iota _v\mathrm{\Omega }\right)F_E+f^{}\mathrm{\Omega }B\right]\text{,}$$

for any $`(v,B)T_{(f,D_E)}𝒞`$.

###### Proposition 7.

The one form $`\mathrm{\Phi }_0`$ on $`𝒞`$ is closed and invariant under the action by $`𝒢`$.

Proof: Recall that there is a universal connection $`𝔻_E`$ over $`C\times 𝒜\left(E\right)`$ whose curvature $`𝔽_E`$ at a point $`(x,D_E)`$ equals,

$`𝔽_E|_{(x,D_E)}`$ $`=(𝔽_E^{2,0},𝔽_E^{1,1},𝔽_E^{0,2})`$
$`\mathrm{\Omega }^2\left(C\right)\mathrm{\Omega }^0\left(𝒜\right)+\mathrm{\Omega }^1\left(C\right)\mathrm{\Omega }^1\left(𝒜\right)+\mathrm{\Omega }^0\left(C\right)\mathrm{\Omega }^2\left(𝒜\right)`$
with

$$𝔽_E^{2,0}=F_E,𝔽_E^{1,1}(v,B)=B\left(v\right),𝔽_E^{0,2}=0,$$

where $`vT_xC`$ and $`B\mathrm{\Omega }^1(C,ad\left(E\right))=T_{D_E}𝒜\left(E\right)`$ (see e.g. ). The Bianchi identity implies that $`Tr𝔽_E`$ is a closed form on $`C\times 𝒜\left(E\right)`$. We also consider the evaluation map,

$$ev:C\times Map(C,M)M$$

$$ev(x,f)=f\left(x\right).$$

It is not difficult to see that the pushforward of the differential form $`ev^{}\left(\mathrm{\Omega }\right)Tr𝔽_E`$ on $`C\times Map(C,M)\times 𝒜\left(E\right)`$ to $`Map(C,M)\times 𝒜\left(E\right)`$ equals $`\mathrm{\Phi }_0`$, i.e.

$$\mathrm{\Phi }_0=_Cev^{}\left(\mathrm{\Omega }\right)Tr𝔽_E\text{.}$$

Therefore the closedness of $`\mathrm{\Phi }_0`$ follows from the closedness of $`\mathrm{\Omega }`$. It is also clear from this description of $`\mathrm{\Phi }_0`$ that it is $`𝒢`$-invariant. $`\mathrm{}`$

From this proposition, we know that $`\mathrm{\Phi }_0=d\mathrm{\Psi }_0`$ locally for some function $`\mathrm{\Psi }_0`$ on $`𝒞`$. As in the Chern-Simons theory, this function $`\mathrm{\Psi }_0`$ can be obtained explicitly by integrating the closed one form $`\mathrm{\Phi }_0`$ along any path joining to a fixed element in $`𝒞`$. When $`M=X\times S^1`$ and $`C=L\times S^1`$, this is essentially the functional used by Thomas in .

From now on, we assume that $`E`$ is a rank one bundle.

###### Lemma 8.

The zeros of $`\mathrm{\Phi }_0`$ are the same as parametrized $``$-SLag cycles in $`M`$.

Proof: Suppose $`(f,D_E)`$ is a zero of $`\mathrm{\Phi }_0`$. By evaluating it on various $`(0,B)`$, we have $`f^{}\mathrm{\Omega }=0`$, i.e. $`f:CM`$ is a parametrized $``$-SLag. This implies that the map

$$\mathrm{}\mathrm{\Omega }:T_{f\left(x\right)}M\mathrm{\Lambda }^2T_x^{}C$$

has image equals $`\mathrm{\Lambda }_+^2T_x^{}C`$, for any $`xC`$. By evaluating $`\mathrm{\Phi }_0`$ on various $`(v,0)`$, we have $`F_E^+=0`$, i.e. $`(f,D_E)`$ is a parametrized $``$-SLag cycle in $`M`$. The converse is obvious. $`\mathrm{}`$

From above results, $`\mathrm{\Phi }_0`$ descends to a closed one form on $`𝒞/𝒢`$, called $`\mathrm{\Phi }`$. Locally we can write $`\mathrm{\Phi }=d`$ for some function $``$ whose critical points are precisely (unparametrized) $``$-SLag cycles in $`M`$. Using the gradient flow lines of $``$, we could formally define a Witten’s Morse homology group, as in the famous Floer’s theory. Roughly speaking one defines a complex $`(𝐂_{},)`$, where $`𝐂_{}`$ is the free Abelian group generated by critical points of $``$ and $``$ is defined by counting the number of gradient flow lines between two critical points of relative index one.

Remark: The equations for the gradient flow are given by

$$\frac{f}{t}=(f^{}\xi F_E),\frac{D_E}{t}=\left(f^{}\mathrm{\Omega }\right),$$

where $`\xi \mathrm{\Omega }^2(M,T_M)`$ is defined by $`\xi (u,v),w=\mathrm{\Omega }(u,v,w)`$.

The equation

$$^2=0$$

requires a good compactification of the moduli space of $``$-SLag cycles in $`M`$, which we are lacking at this moment (see  however). We denote this proposed homology group as $`H_C\left(M\right)`$, or $`H_C(M,\alpha )`$ when $`f_{}\left[C\right]=\alpha H_4(M,)`$.

This homology group should be invariant under deformations of the almost $`G_2`$-metric on $`M`$ and its Euler characteristic equals,

$$\chi \left(H_C\left(M\right)\right)=\mathrm{\#}^{SLag}\left(M\right)\text{.}$$

Like Floer homology groups, they measure the middle dimensional topology of the configuration space $`𝒞`$ divided by $`𝒢`$.

## 4 TQFT of $``$-SLag cycles

In this section we study complete almost $`G_2`$-manifold $`M_i`$ with asymptotically cylindrical ends and the behavior of $`H_C\left(M\right)`$ when a closed almost $`G_2`$-manifold $`M`$ decomposes into connected sum of two pieces, each with an asymptotically cylindrical end,

$$M=M_1\underset{𝑋}{\mathrm{\#}}M_2.$$

Nontrivial examples of compact $`G_2`$-manifolds are constructed by Kovalev  using such connected sum approach. The boundary manifold $`X`$ is necessary a Calabi-Yau threefold. We plan to discuss analytic aspects of $`M_i`$’s in a future paper .

Each $`M_i`$’s will define a Lagrangian subspace $`_{M_i}`$ in the moduli space of special Lagrangian cycles in $`X`$. Furthermore we expect to have a gluing formula expressing the above homology group for $`M`$ in terms of the Floer Lagrangian intersection homology group for the two Lagrangian subspaces $`_{M_1}`$ and $`_{M_2}`$,

$$H_C\left(M\right)=HF_{Lag}^{^{SLag}\left(X\right)}(_{M_1},_{M_2})\text{.}$$

These properties can be reformulated to give us a topological quantum field theory. To begin we have the following definition.

###### Definition 9.

An almost $`G_2`$-manifold $`M`$ is called cylindrical if $`M=X\times ^1`$ and its positive three form respect such product structure, i.e.

$$\mathrm{\Omega }_0=\mathrm{Re}\mathrm{\Omega }_X+\omega _Xdt\text{.}$$

A complete almost $`G_2`$-manifold $`M`$ with one end $`X\times [0,\mathrm{})`$ is called asymptotically cylindrical if the restriction of its positive three form equals to the above one for large $`t`$, up to a possible error of order $`O\left(e^t\right)`$. More precisely the positive three form $`\mathrm{\Omega }`$ of $`M`$ restricted to its end equals,

$$\mathrm{\Omega }=\mathrm{\Omega }_0+d\zeta $$

for some two form $`\zeta `$ satisfying $`\left|\zeta \right|+\left|\zeta \right|+\left|^2\zeta \right|+\left|^3\zeta \right|Ce^t.`$

Remark: If $`M`$ is an almost $`G_2`$-manifold with an asymptotically cylindrical end $`X\times [0,\mathrm{})`$, then $`(X,\omega _X,\mathrm{\Omega }_X)`$ is a complex threefold with a trivial canonical line bundle, but the Kähler form $`\omega _X`$ might not be Einstein. This is so, i.e. a Calabi-Yau threefold, provided that $`M`$ is a $`G_2`$-manifold. We will simply write $`M=X`$.

We consider $``$-SLags $`C`$ in $`M`$ which satisfy a Neumann condition at infinity. That is, away from some compact set in $`M`$, the immersion $`f:CM`$ can be written as

$$f:L\times [0,\mathrm{})X\times [0,\mathrm{})$$

with $`f/t`$ vanishes at infinite . A relative $``$-SLag itself has asymptotically cylindrical end $`L\times [0,\mathrm{})`$ with $`L`$ a special Lagrangian submanifold in $`X`$. A relative $``$-SLag cycle in $`M`$ is a pair $`(C,D_E)`$ with $`C`$ a relative $``$-SLag in $`M`$ and $`D_E`$ a unitary connection over $`C`$ with finite energy,

$$_C\left|F_E\right|^2𝑑v<\mathrm{}\text{.}$$

Any finite energy connection $`D_E`$ on $`C`$ induces a unitary flat connection $`D_E^{}`$ on $`L`$ .

Such a pair $`(L,D_E^{})`$ of a unitary flat connection $`D_E^{}`$ over a special Lagrangian submanifold $`L`$ in a Calabi-Yau threefold $`X`$ is called a special Lagrangian cycle in $`X`$. Their moduli space $`^{SLag}\left(X\right)`$ plays an important role in the Strominger-Yau-Zaslow Mirror Conjecture  or . The tangent space to $`^{SLag}\left(X\right)`$ is naturally identified with $`H^2(L,)\times H^1(L,ad\left(E^{}\right))`$. For line bundles over $`L`$, the cup product

$$:H^2(L,)\times H^1(L,),$$

induces a symplectic structure on $`^{SLag}\left(X\right)`$ . Using analytic results from  about asymptotically cylindrical manifolds, we can prove the following theorem.

###### Claim 10.

Suppose $`M`$ is an asymptotically cylindrical (almost) $`G_2`$-manifold with $`M=X`$. Let $`^{SLag}\left(M\right)`$ be the moduli space of rank one relative $``$-SLag cycles in $`M`$. Then the map defined by the boundary values,

$$b:^{SLag}\left(M\right)^{SLag}\left(X\right),$$

is a Lagrangian immersion.

Sketch of the proof (): For any closed Calabi-Yau threefold $`X`$ (resp. $`G_2`$-manifold $`M`$), the moduli space of rank one special Lagrangian submanifolds $`L`$ (resp. $``$-SLags $`C`$) is smooth  and has dimension $`b^2\left(L\right)`$ (resp. $`b_+^2\left(C\right)`$). The same holds true for complete manifold $`M`$ with a asymptotically cylindrical end $`X\times [0,\mathrm{})`$, where $`b_+^2\left(C\right)_{L^2}`$ denote the dimension of $`L^2`$-harmonic self-dual two forms on a relative $``$-SLag $`C`$ in $`M`$.

The linearization of the boundary value map $`^{SLag}\left(M\right)^{SLag}\left(X\right)`$ is given by $`H_+^2\left(C\right)_{L^2}\stackrel{𝛼}{}H^2\left(L\right)`$. Similar for the connection part, where the boundary value map is given by $`H^1\left(C\right)_{L^2}\stackrel{𝛽}{}H^1\left(L\right)`$. We consider the following diagram where each row is a long exact sequence of $`L^2`$-cohomology groups for the pair $`(C,L)`$ and each column in a perfect pairing.

$$\begin{array}{cccccccccccc}0& & H_+^2(C,L)& & H_+^2\left(C\right)& \stackrel{𝛼}{}& H^2\left(L\right)& & H^3(C,L)& & \mathrm{}& \\ & & & & & & & & & & & \\ 0& & H_+^2\left(C\right)& & H_+^2(C,L)& & H^1\left(L\right)& \stackrel{𝛽}{}& H^1\left(C\right)& & \mathrm{}& \\ & & & & & & & & & & & \\ & & & & & & & & & & & \end{array}$$

Notice that $`H_+^2(C,L)`$, $`H_+^2\left(C\right)`$ and $`H^2\left(L\right)`$ parametrize infinitesimal deformation of $`C`$ with fixed $`C`$, deformation of $`C`$ alone and deformation of $`L`$ respectively.

By simple homological algebra, it is not difficult to see that $`\mathrm{Im}\alpha \mathrm{Im}\beta `$ is a Lagrangian subspace of $`H^2\left(L\right)H^1\left(L\right)`$ with the canonical symplectic structure. Hence the result. $`\mathrm{}`$

Remark: The deformation theory of conical special Lagrangian submanifolds is developed by Pacini in .

We denote the immersed Lagrangian submanifold $`b\left(^{SLag}\left(M\right)\right)`$ in $`^{SLag}\left(X\right)`$ by $`_M`$. When $`M`$ decompose as a connected sum $`M_1\mathrm{\#}_XM_2`$ along a long neck, as in Atiyah’s conjecture on Floer Chern-Simons homology group , we expect to have an isomorphism,

$$H_C\left(M\right)HF_{Lag}^{^{SLag}\left(X\right)}(_{M_1},_{M_2})\text{.}$$

More precisely, suppose $`\mathrm{\Omega }_t`$ with $`t[0,\mathrm{})`$, is a family of $`G_2`$-structure on $`M_t=M`$ such that as $`t`$ goes to infinite, $`M`$ decomposes into two components $`M_1`$ and $`M_2`$, each has an aymptotically cylindrical end $`X\times [0,\mathrm{})`$. Then we expect that $`lim_t\mathrm{}H_C\left(M_t\right)HF_{Lag}^{^{SLag}\left(X\right)}(_{M_1},_{M_2})`$. We summarize these structures in the following table:

| Manifold: | (almost) $`G_2`$ -manifold, $`M^7`$ | (almost) CY threefold, $`X^6`$ | $`\begin{array}{c}\end{array}`$ |
| --- | --- | --- | --- |
| SUSY Cycles: | $``$ -SLag. submfds.+ ASD bdl | SLag submfds.+ flat bdl | $`\begin{array}{c}\end{array}`$ |
| Invariant: | Homology group, $`H_C\left(M\right)`$ | Fukaya category, $`Fuk\left(^{SLag}\left(X\right)\right).`$ | $`\begin{array}{c}\end{array}`$ |

These associations can be formalized to form a TQFT . Namely we associate an additive category $`F\left(X\right)=Fuk\left(^{SLag}\left(X\right)\right)`$ to a closed almost Calabi-Yau threefold $`X`$, a functor $`F\left(M\right):F\left(X_0\right)F\left(X_1\right)`$ to an almost $`G_2`$-manifold $`M`$ with asymptotically cylindrical ends $`X_1X_0=X_1\overline{X}_0`$. They satisfy

| (i) | $`F\left(\varphi \right)=\text{the additive tensor category of vector spaces }\left(\left(Vec\right)\right)\text{,}`$ |
| --- | --- |
| (ii) | $`F\left(X_1X_2\right)=F\left(X_1\right)F\left(X_2\right).`$ |

For example, when $`M`$ is a closed $`G_2`$-manifold, that is a cobordism between empty manifolds, then we have $`F\left(M\right):\left(\left(Vec\right)\right)\left(\left(Vec\right)\right)`$ and the image of the trivial bundle is our homology group $`H_C\left(M\right)`$.

## 5 More TQFTs

Notice that all TQFTs we propose in this paper are formal mathematical constructions. Besides the lack of compactness for the moduli spaces, the obstruction issue is also a big problem if we try to make these theories rigorous. This problem is explained to the author by a referee.

There are other TQFTs naturally associated to Calabi-Yau threefolds and $`G_2`$-manifolds but (1) they do not involve nontrivial coupling between submanifolds and bundles and (2) new difficulties arise because of corresponding moduli spaces for Calabi-Yau threefolds have virtual dimension zero and could be singular. They are essentially in the paper by Donaldson and Thomas .

TQFT of associative cycles

We assume that $`M`$ is a $`G_2`$-manifold, i.e. $`\mathrm{\Omega }`$ is parallel rather than closed. Three dimensional submanifolds $`A`$ in $`M`$ calibrated by $`\mathrm{\Omega }`$ is called associative submanifolds and they can be characterized by $`\chi |_A=0`$ () where $`\chi \mathrm{\Omega }^3(M,T_M)`$ is defined by $`w,\chi (x,y,z)=\mathrm{\Omega }(w,x,y,z)`$. We define a parametrized A-cycle to be a pair $`(f,D_E)𝒞_A=Map(A,M)\times 𝒜\left(E\right),`$ with $`f:AM`$ a parametrized A-submanifold and $`D_E`$ is a unitary flat connection on a Hermitian vector bundle $`E`$ over $`A`$. There is also a natural $`𝒢`$-invariant closed one form $`\mathrm{\Phi }_A`$ on $`𝒞_A`$ given by

$$\mathrm{\Phi }_A(f,D_E)(v,B)=_ATrF_EB+f^{}\chi ,v_{T_M},$$

for any $`(v,B)\mathrm{\Gamma }(A,f^{}T_M)\times \mathrm{\Omega }^1(A,ad\left(E\right))=T_{(f,D_E)}𝒞_A`$ . Its zero set is the moduli space of A-cycles in $`M`$. As before, we could formally apply arguments in Witten’s Morse theory to $`\mathrm{\Phi }_A`$ and define a homology group $`H_A\left(M\right)`$.

The corresponding category associated to a Calabi-Yau threefold $`X`$ would be the Fukaya-Floer category of the moduli space of unitary flat bundles over holomorphic curves in $`X`$, denote $`^{curve}\left(X\right)`$. We summarize these in the following table:

| Manifold: | $`G_2`$ -manifold, $`M^7`$ | CY threefold, $`X^6`$ | $`\begin{array}{c}\end{array}`$ |
| --- | --- | --- | --- |
| SUSY Cycles: | A-submfds.+ flat bundles | Holomorphic curves+ flat bundles | $`\begin{array}{c}\end{array}`$ |
| Invariant: | Homology group, $`H_A\left(M\right)`$ | Fukaya category, $`Fuk\left(^{curve}\left(X\right)\right).`$ | $`\begin{array}{c}\end{array}`$ |

TQFT of Donaldson-Thomas bundles

We assume that $`M`$ is a seven manifold with a $`G_2`$-structure such that its positive three form $`\mathrm{\Omega }`$ is co-closed, rather than closed, i.e. $`d\mathrm{\Theta }=0`$ with $`\mathrm{\Theta }=\mathrm{\Omega }`$. In  Donaldson and Thomas introduce a first order Yang-Mills equation for $`G_2`$-manifolds,

$$F_E\mathrm{\Theta }=0\text{.}$$

Their solutions are the zeros of the following gauge invariant one form $`\mathrm{\Phi }_{DT}`$ on $`𝒜\left(E\right)`$,

$$\mathrm{\Phi }_{DT}\left(D_E\right)\left(B\right)=_MTr\left[F_EB\right]\mathrm{\Theta }\text{,}$$

for any $`B\mathrm{\Omega }^1(M,ad\left(E\right))=T_{D_E}𝒜\left(E\right)`$. This one form $`\mathrm{\Phi }_{DT}`$ is closed because of $`d\mathrm{\Theta }=0`$. As before, we can formally define a homology group $`H_{DT}\left(M\right)`$. The corresponding category associated to a Calabi-Yau threefold $`X`$ should be the Fukaya-Floer category of the moduli space of Hermitian Yang-Mills connections over $`X`$, denote $`^{HYM}\left(X\right)`$. Again we summarize these in a table:

| Manifold: | $`G_2`$ -manifold, $`M^7`$ | CY threefold, $`X^6`$ | $`\begin{array}{c}\end{array}`$ |
| --- | --- | --- | --- |
| SUSY Cycles: | DT-bundles | Hermitian YM-bundles | $`\begin{array}{c}\end{array}`$ |
| Invariant: | Homology group, $`H_{DT}\left(M\right)`$ | Fukaya category, $`Fuk\left(^{HYM}\left(X\right)\right).`$ | $`\begin{array}{c}\end{array}`$ |

It is an interesting problem to understand the transformations of these TQFTs under dualities in M-theory.

Acknowledgments: This paper is partially supported by NSF/DMS-0103355. The author expresses his gratitude to J.H. Lee, R. Thomas, A. Voronov and X.W. Wang for useful discussions. The author also thank the referee for many useful comments.


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# Direct evidence for two-band superconductivity in MgB2 single crystals from directional point-contact spectroscopy in magnetic fields

## Abstract

We present the results of the first directional point-contact spectroscopy experiments in high-quality MgB2 single crystals. Due to the directionality of the current injection into the samples, the application of a magnetic field allowed us to separate the contributions of the $`\sigma `$ and $`\pi `$ bands to the total conductance of our point contacts. By using this technique, we were able to obtain the temperature dependency of each gap independent of the other. The consequent, strong reduction of the error on the value of the gap amplitude as function of temperature allows a stricter test of the predictions of the two-band model for MgB2.

During the last year, the consensus has been growing within the scientific community on the fact that most of the features of MgB2 discovered so far can be properly explained by admitting that two band systems are present in this new superconductor: quasi-2D $`\sigma `$ bands arising from hybrid $`sp^2`$ orbitals in the boron planes, and 3D $`\pi `$ bands that stem from the out-of-plane $`p_\mathrm{z}`$ orbitals twobands ; Choi . The unusual consequence of this band structure is that two different energy gaps can be observed in clean limit Choi ; Liu ; Brinkman : $`\mathrm{\Delta }_\sigma `$ (the larger) and $`\mathrm{\Delta }_\pi `$ (the smaller). Both gaps are expected to close at the same temperature $`T_\mathrm{c}`$ because of an inter-band pair-scattering mechanism Suhl  but, while $`\mathrm{\Delta }_\sigma (T)`$ should approximately follow a BCS-like curve, a marked reduction of $`\mathrm{\Delta }_\pi (T)`$ with respect to a BCS-like behavior is expected at $`T`$20 K Liu ; Brinkman .

So far, one of the most convincing experimental supports of this model has been the observation of two gaps by tunneling tunnel  and point-contact spectroscopy Szabo  in polycrystal samples and films. However, a direct and accurate test of the predictions of the two-band model has been so far impossible due to the lack of high-quality single crystals large enough to be used for direction-controlled point-contact and tunnel spectroscopy.

In this Letter, we present the results of the first directional point-contact measurements in large single crystals of MgB2. We injected current along the $`ab`$ plane or along the $`c`$ axis, and applied a magnetic field either parallel or perpendicular to the $`ab`$ planes. This allowed us to separate the partial contributions of the $`\sigma `$ and $`\pi `$ bands to the total conductance, and to fit them obtaining the temperature dependency of each gap with great accuracy. We will show that all the results of this technique confirm very well the predictions of the two-band model.

The high-quality MgB2 single crystals used for our point-contact experiments were produced at ETH (Z$`\ddot{\mathrm{u}}`$rich) by starting from a mixture of Mg and B. This mixture was put into a BN container and the crystals were grown at a pressure of 30-35 kbar in a cubic anvil device. The thermal process includes a one-hour heating up to 1700-1800C, a plateau of 1-3 hours, and a final cooling lasting 1-2 hours. MgB2 plate-like crystals up to 200 $`\mu `$g in weight and $`1.5\times 0.9\times 0.2`$ mm3 in size can be obtained by using this technique, even though the crystals used in our measurements were smaller ($`0.6\times 0.6\times 0.04`$ mm3 at most). The crystals were etched with 1% HCl in dry ethanol to remove possible deteriorated surface layers. The critical temperature of the crystals, measured by AC susceptibility, is $`T_\mathrm{c}=38.2`$ K with $`\mathrm{\Delta }T_\mathrm{c}0.2`$ K.

Using Au or Pt tips to make point contacts did not ensure mechanical stability during thermal cycling and reproducibility of the conductance curves. Thus, we moved to a non-conventional technique that consists in using as a counterelectrode either a very small ($`50\mu `$m) drop of Ag conductive paint, or a small piece of indium pressed on the surface of the sample. With this technique, a control of the contact characteristics is possible anyway, by applying short voltage pulses to the junction. The apparent contact area is much greater than that required to have ballistic current flow ballistic , but the *effective* electrical contact occurs in a much smaller region, due to the presence of parallel micro-bridges in the spot area. On the other hand, the resistance of all our contacts was in the range $`10÷50\mathrm{\Omega }`$. This, together with the estimated mean free path for the same crystals $`\mathrm{}=80`$nm Sologubenko , proves that our contacts are in the ballistic regime. The contacts were positioned on the crystal surfaces so as to inject the current along the $`c`$ axis or along the $`ab`$ planes. The directionality of current injection is ensured by the small roughness of the crystal surfaces even on a microscopic scale. Figures 1(a) and (b) report AFM measurements on the $`ab`$-plane surface, after removal of the In contact; the surfaces perpendicular to the $`ab`$ plane are even smoother.

Figure 1(c) shows some examples of the low-temperature *normalized* conductances d$`I/`$d$`V`$ of contacts with current injection either parallel or perpendicular to the $`ab`$ plane. All the conductance curves shown in the present Letter were normalized by dividing the measured d$`I/`$d$`V`$ data by the linear or quartic function that best fits them for $`|V|>30`$ meV. The $`ab`$-plane curves clearly show two peaks at $`V\pm 2.7`$ mV and $`V\pm 7.2`$ mV, while the $`c`$-axis curves only show a peak at $`V\pm (2.8÷3.5)`$ mV and a smooth shoulder at $`V\pm 7.2`$ mV. These features, marked by dashed lines in the figure, are clearly related to the two gaps $`\mathrm{\Delta }_\pi `$ and $`\mathrm{\Delta }_\sigma `$. Solid lines are the best-fitting curves calculated by using the BTK model BTK  generalized to the case of two bands, in which the normalized conductance $`\sigma `$ is given by: $`\sigma =w_\pi \sigma _\pi +(1w_\pi )\sigma _\sigma `$. Here, $`\sigma _\pi `$ and $`\sigma _\sigma `$ are the normalized conductances for the $`\pi `$ and $`\sigma `$ bands, respectively, and $`w_\pi `$ is the weight of the $`\pi `$ band, that depends on the angle $`\phi `$ between the direction of current injection and the boron planes Brinkman . The fit is almost perfect, especially at low voltage, but it must be said that there are 7 adjustable parameters: the gaps $`\mathrm{\Delta }_\sigma `$ and $`\mathrm{\Delta }_\pi `$, the broadening parameters $`\mathrm{\Gamma }_\sigma `$ and $`\mathrm{\Gamma }_\pi `$, the barrier height coefficients $`Z_\sigma `$ and $`Z_\pi `$, plus the weight factor $`w_\pi `$. The normalization may yield additional uncertainty on $`\mathrm{\Gamma }_{\sigma ,\pi }`$ and $`Z_{\sigma ,\pi }`$ but does not affect the gap values.

Figures 2(a) and 2(b) show the temperature dependency of the normalized conductance curves (circles) of Ag-paint and In point contacts, respectively. The current was mainly injected along the $`ab`$ planes in (a), and parallel to the $`c`$ axis in (b). At the increase of the temperature, the typical two-gap features shown in Fig. 1 merge in a broad maximum, which disappears at the $`T_\mathrm{c}`$ of the junction that fell in all cases between 34.1 and 37.6 K. Since neither the current direction nor the contact resistance depend on the temperature, in fitting the conductances at various temperatures we kept both $`w_\pi `$ and the barrier parameters $`Z_\sigma `$ and $`Z_\pi `$ equal to their low-$`T`$ values, thus reducing the actual adjustable parameters to 4. The best-fit curves are shown in Fig. 2 as solid lines.

The inset of Fig. 2 reports the temperature dependency of the two gaps, obtained by fitting the conductance curves of two $`ab`$-plane contacts (solid symbols) and of two $`c`$-axis contacts (open symbols). For clarity, error bars are only shown for a data set in the $`ab`$-plane-current case, but they are of the same order of magnitude in the $`c`$-axis cases. The relevant barrier parameters (independent of temperature) are $`Z_\sigma =0.5÷1.4`$ and $`Z_\pi =0.3÷0.8`$ depending on the junction, while the broadening parameters $`\mathrm{\Gamma }_{\sigma ,\pi }`$ increase with $`T`$ always remaining in the range between 0.5 and 3 meV. An important result is that the average values of the $`\pi `$-band weight factor resulting from the fits ($`w_\pi =0.75\pm 0.03`$ for $`ab`$-plane current, and $`w_\pi =0.980\pm 0.005`$ for $`c`$-axis current) are in very good agreement with the values predicted by the two-band model ($`w_\pi =0.66`$ and $`w_\pi =0.99`$, respectively Brinkman ). The small mismatch that actually exists can be ascribed to the fact that, in our low-barrier contacts, the current is injected within a finite solid angle. The integration of the theoretical $`w_\pi (\phi )`$, taking into account the $`\mathrm{cos}\phi `$ dependency of the electron injection probability, shows that our experimental values of $`w_\pi `$ are compatible with cone apertures of about $`26^{}`$ and $`60^{}`$, respectively.

The average low-temperature gap values $`\mathrm{\Delta }_\sigma =7.1\pm 0.5`$ meV and $`\mathrm{\Delta }_\pi =2.9\pm 0.3`$ meV agree very well with the theoretical values predicted by the two-band model Choi ; Brinkman . Nevertheless, at $`T/T_\mathrm{c}0.5`$ the experimental uncertainty on the gap value increases so much that it becomes practically impossible to determine whether the $`\mathrm{\Delta }_\pi (T)`$ and $`\mathrm{\Delta }_\sigma (T)`$ curves strictly follow a BCS-like curve or not. Clearly, this problem is also present in all the previous point-contact or tunneling experiments in which the temperature dependency of the gaps was obtained.

A careful and reliable test of the predictions of the two-band model obviously requires a more accurate determination of the gaps and their temperature dependency. Only by reducing the number of free fitting parameters, e.g. by separating the contributions of the two bands to the total conductance, this goal might be obtained. On the basis of some point-contact results obtained by Szabó *et al.* Szabo  in polycrystalline samples exposed to magnetic fields, we developed a technique that combines the selective removal of one gap with the directional point-contact spectroscopy. By applying to each junction (at low temperature) magnetic fields of increasing intensity, either parallel to the $`c`$ axis or to the $`ab`$ planes, we observed in both cases the complete vanishing of the small-gap features in the conductance when $`B1`$ T. This effect is clearly visible in Figure 3, that shows the magnetic field-dependency at 4.2 K of the conductance of $`ab`$-plane contacts in a field parallel to the $`c`$ axis (a) and parallel to the $`ab`$ plane (b). The crucial point here is to show that a field of 1 T is enough to remove superconductivity in the $`\pi `$ band without modifying the conductance of the $`\sigma `$ band up to a temperature close to $`T_\mathrm{c}`$. Actually, the effect of the field on the large gap depends on the field direction. Figure 3(b) shows that, when $`𝐁ab`$ plane, the large-gap features remain clearly distinguishable up to 9 T, with only some marks of gap closing. Instead, when $`𝐁c`$ axis (a), the peaks due to the large gap merge together at $`B4`$ T giving rise to a broad maximum. In addition to this, if the field only slightly exceeds 1 T the conductance curves remain practically unchanged (see Fig. 3). These results demonstrate that: i) the $`\pi `$ band is quite isotropic and its critical field at 4.2 K is around 1 T; ii) the $`\sigma `$ band is anisotropic and, at 4.2 K, $`\mathrm{\Delta }_\sigma `$ is unaffected by a field of 1 T parallel to the $`ab`$ plane; iii) the $`\sigma `$-band critical field parallel to $`ab`$ is rather high ($`>9`$ T) at low temperature, in agreement with other results on similar samples campocritico1 . In addition to this, some preliminary measurements we made in $`c`$-axis contacts with $`𝐁ab`$ at about 30 K have shown that $`𝐁_{\mathrm{c2}\mathrm{ab}}^\sigma 3.5`$ T. A detailed discussion of the temperature dependency of the critical fields determined by our Andreev reflection experiments will be given in a forthcoming paper nostro . Nevertheless, on the basis of the aforementioned results, we can be confident that a field of 1 T parallel to the $`ab`$ planes is too weak to affect seriously the large gap, even at temperatures close to $`T_\mathrm{c}`$. This hypothesis will be confirmed by the $`\mathrm{\Delta }_\sigma (T)`$ curve (see Fig. 5(c)) that shows a BCS-like behavior with no anomalous high-$`T`$ gap suppression due to the field.

As a consequence, we measured the conductance of a In-MgB2 $`c`$-axis contact at 4.6 K, with no field (see Figure 4, open circles) and with a field of 1 T parallel to the $`ab`$ planes (see Figure 4, light gray circles). When the magnetic field destroys the gap in the $`\pi `$ band, the *normalized* conductance becomes: $`\sigma (B=1\mathrm{T})=w_\pi +(1w_\pi )\sigma _\sigma `$. This function contains only three free parameters: $`\mathrm{\Delta }_\sigma `$, $`\mathrm{\Gamma }_\sigma `$ and $`Z_\sigma `$, whose best-fit values at $`T=4.6`$ K are 7.1 meV, 1.7 meV and 0.6, respectively. In fact, we took $`w_\pi =0.98`$, that is the value obtained from the fit of the total $`c`$-axis conductance at the same temperature. An independent determination of the small gap can be obtained by subtracting the conductance curve measured in the presence of the field from that measured without field. The resulting curve, vertically shifted by one unit, is reported in Fig. 4 (dark gray circles). The result of the subtraction can be expressed by the functional form $`\sigma (B=0)\sigma (B=1\mathrm{T})=w_\pi (\sigma _\pi 1)`$. Fitting the experimental data to this function (again, with $`w_\pi =0.98`$) allows determining the three remaining free parameters $`\mathrm{\Delta }_\pi `$, $`\mathrm{\Gamma }_\pi `$ and $`Z_\pi `$, that assume at $`T=4.6`$ K the values 2.8 meV, 2 meV and 0.6, respectively. Incidentally, the very good quality of the fits (solid lines in Fig. 4) further shows that the value of $`w_\pi `$ is appropriate. Fig. 5 reports the temperature dependency of the curves already shown at 4.6 K in Fig. 4: the $`c`$-axis conductance in a field of 1 T parallel to the $`ab`$ planes, $`\sigma (B=1\mathrm{T})`$ (a) and the difference $`\sigma (B=0)\sigma (B=1\mathrm{T})`$ (b), with the relevant best-fitting curves (solid lines). Notice that the difference curves look particularly “clean” and noise-free since the subtraction also allows eliminating some experimental fluctuations that are present both in $`\sigma (B=0)`$ and in $`\sigma (B=1\mathrm{T})`$. The resulting fits are quite good at any temperature and in the whole voltage range. Finally, the temperature dependency of both the large and the small gap obtained from this fitting procedure is reported in Figure 5(c). A comparison with the inset of Fig. 2 clearly shows that the separate fitting of the partial conductances allows a strong reduction of the error bars (evaluated from the fitting procedure) and a consequent improvement of the accuracy. In particular, the error affecting $`\mathrm{\Delta }_\pi `$ is very small even at $`T`$ close to $`T_\mathrm{c}`$, so that the deviation of the gap values from the BCS-like curve (dashed line) results to be much larger than the experimental uncertainty.

In conclusion, we have shown that a technique which combines directional point-contact spectroscopy with the selective removal of the $`\pi `$-band gap by a magnetic field not only proves the existence of two gaps in MgB2, but also allows a very accurate test of the predictions of the two-band model. In particular, by fitting the zero-field conductance curves of directional point contacts, we obtained the weights of the $`\sigma `$ and $`\pi `$ bands, which resulted in good agreement with those predicted theoretically both for $`c`$-axis and $`ab`$-plane current injection. Then, we separately analyzed the partial conductances $`\sigma _\sigma `$ and $`\sigma _\pi `$, getting the most accurate values of the gaps in MgB2 obtained so far: at low $`T`$, $`\mathrm{\Delta }_\sigma =7.1\pm 0.1`$ meV and $`\mathrm{\Delta }_\pi =2.80\pm 0.05`$ meV. We also found that, while $`\mathrm{\Delta }_\sigma `$ follows a BCS-like temperature evolution, $`\mathrm{\Delta }_\pi `$ deviates from the BCS behavior at $`T>25`$ K, in very good agreement with the two-band model. Due to the small error affecting the gap value, this deviation is here unquestionably determined for the first time.

This work was supported by the INFM Project PRA-UMBRA and by the INTAS project “Charge transport in metal-diboride thin films and heterostructures”.


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# Electron and orbital correlations in Ca2-xSrxRuO4 probed by optical spectroscopy

## Abstract

The doping and temperature dependent optical conductivity spectra of the quasi-two-dimensional Ca2-xSrxRuO4 (0.0$``$x$``$2.0) system were investigated. In the Mott insulating state, two electron correlation-induced peaks were observed around 1.0 and 1.9 eV, which could be understood in terms of the 3-orbital Hubbard model. The low frequency peak showed a shift toward higher frequency as temperature was lowered, which indicated that electron-phonon interactions play an important role in the orbital arrangements. From the systematic analysis, it was suggested that the antiferro-orbital and the ferro-orbital ordering states could coexist.

The discovery of unconventional superconductivity in Sr2RuO4 has stimulated great interest in layered perovskite Ca2-xSrxRuO4 (0.0$``$x$``$2.0) (CSRO) . The normal state of Sr2RuO4 can be described as a quasi-two dimensional Fermi-liquid ; however, the isovalent Ca substitution for Sr gives rise to a Mott insulator Ca2RuO4 . As x decreases, the RuO6 octahedra rotate and become flattened . These structural distortions decrease the Ru 4$`d`$ bandwidth $`W`$, which leads to a Mott gap. Therefore, CSRO can be used as a prototype material system to investigate the evolution of electronic structures from a band metal to a Mott insulator.

The role of the orbital degrees of freedom in Ca2RuO4 has provided us with a challenge of scientific interest. The Ru ion has a formal valency of 4+ with four $`t_{2g}`$ electrons. At an early stage, it was proposed that the $`d_{xy}`$ orbitals should be fully occupied and that a Mott gap becomes open between the half-filled $`d_{yz/zx}`$ states . However, recent x-ray absorption spectroscopy (XAS) data revealed that both $`d_{xy}`$ and $`d_{yz/zx}`$ orbitals remain partially filled down to low temperature ($`T`$) . Then, it would be difficult to understand how the Mott insulator can be formed with partially filled $`d_{xy}`$, $`d_{yz}`$, and $`d_{zx}`$ orbitals. More recently, using the 3-orbital Hubbard model, Hotta and Dagotto suggested that the unusual orbital occupancy could be explained by an antiferro-orbital (AFO) ordering in the antiferromagnetic (AFM) state .

Optical spectroscopy has been used as a powerful method to investigate electronic structures of numerous strongly correlated materials . However, most of the observed correlation-induced features have been interpreted in terms of the single-band Hubbard model without considering the orbital degeneracy. Recently, optical spectroscopy was applied to probe the role of orbital ordering in polaron absorption of perovskite manganites; even with similar orbital occupancy, optical absorption can vary significantly depending on the orbital correlation between nearest neighbors . Therefore, optical spectroscopy can provide us with a way to investigate the role of orbitals in the intriguing electronic states of CSRO.

In this Letter, we investigate the doping- and $`T`$-dependent optical conductivity spectra $`\sigma (\omega )`$ of CSRO. In the insulating state, $`\sigma (\omega )`$ show two correlation-induced excitations around 1.0 and 1.9 eV. These features are explained in terms of the 3-orbital Hubbard model, which considers the $`t_{2g}`$ orbital multiplicity. In the Mott insulating state, the AFO correlation is prevalent, but the ferro-orbital (FO) correlation seems to coexist with decrease of $`T`$. It is also found that the electron-phonon interaction plays an important role in the $`T`$-dependent evolution of the orbital arrangements.

High-quality CSRO single crystals were grown by the floating zone method. Details of the crystal growth and characterization were described elsewhere . Near normal incident reflectivity spectra, $`R(\omega )`$, of the $`ab`$-plane were measured between 5 meV and 30 eV. Using a liquid He-cooled cryostat, $`T`$-dependent $`R(\omega )`$ were obtained below 5.0 eV. Using Kramers-Kronig analysis, $`\sigma (\omega )`$ were obtained .

Figure 1 shows $`\sigma (\omega )`$ of CSRO at room $`T`$. For Sr2RuO4, $`\sigma (\omega )`$ has a strong Drude-like peak, indicating its metallic state. As x decreases, the Drude-like peak becomes gradually suppressed. For Ca2RuO4, $`\sigma (\omega )`$ shows an insulating response with an optical gap. These spectral changes are consistent with the metal-insulator (MI) transition observed in dc resistivity $`\rho _{dc}`$ . The strong peak around 3.0 eV can be assigned to the $`p`$-$`d`$ transition from the O 2$`p`$ to the unoccupied Ru $`t_{2g}`$ states, just like in earlier works on numerous ruthenates . Therefore, the spectral features below 2.5 eV should originate from transitions between the Ru 4$`d`$ bands.

The spectral weight changes in Fig. 1 can be understood according to the Mott-Hubbard picture. As x decreases, the structural distortions become larger , which makes $`W`$ of the Ru 4$`d`$ orbitals narrower. As $`U/W`$ increases ($`U`$ is the electron correlation energy.), the Hubbard bands develop with reduction of the quasi-particle peak centered at the Fermi energy . Figure 1 shows that an additional peak develops around 2.0 eV as x decreases. To identify this peak more easily, each spectrum is subtracted by $`\sigma (\omega )`$ of x=2.0 and plotted as $`\mathrm{\Delta }\sigma (\omega )`$ in the inset of Fig. 1. The spectral weight redistributions between the coherent and the incoherent excitations can be understood in the $`W`$-controlled Mott-Hubbard picture. Then, the 2.0 eV excitation should be assigned as the so-called $`\mathrm{`}U`$-peak’, i.e., the optical transition from the lower Hubbard band to the upper Hubbard band.

The increase of $`U/W`$ should lead to an AFM Mott insulator. For its $`\sigma (\omega )`$, only one correlation-induced peak was usually reported . However, $`\sigma (\omega )`$ of the x=0.0 sample exhibits two separate peaks around 1.0 and 1.9 eV. Earlier, Puchkov et al. reported $`\sigma (\omega )`$ of Ca2RuO4 up to 1.3 eV and assigned the low energy peak to the $`U`$ peak . The high energy peak corresponds to the 2.0 eV excitation in the metallic CSRO. If both peaks come from the electron correlation effects, the single-band Hubbard model cannot explain the appearance of these two peaks. Moreover, the simple picture cannot explain the recent XAS studies, which reported a dramatic redistribution of orbital occupancies .

To obtain further insights, we investigated $`\sigma (\omega )`$ of the x=0.06 sample, which undergoes an MI transition below room $`T`$ . The inset of Fig. 2(a) shows that $`\rho _{dc}`$ experiences an abrupt jump at $`T_{MI}`$ 220 K with decreasing $`T`$, which is closely related to the first-order structural transition . Figure 2(a) shows the $`T`$-dependent $`\sigma (\omega )`$, where the sharp spikes below 0.1 eV are due to transverse optic phonons. Consistent with $`\rho _{dc}`$, $`\sigma (\omega )`$ also show the first-order nature of the MI transition; below $`T_{MI}`$, the strong coherent peak suddenly disappears and an optical gap appears with the 1.0 eV peak (Peak $`\alpha `$), accompanied by a slight enhancement of the 1.9 eV peak (Peak $`\beta `$). The new Peak $`\alpha `$ does exist in the insulating region of the x=0.06 sample as well as in the room-$`T`$ $`\sigma (\omega )`$ of the x=0.0 sample. \[Note that $`T_{MI}`$ for the x=0.0 sample is around 357 K .\] Thus, the two-peak structure can be regarded as an ubiquitous feature of the Mott insulating state in CSRO.

Note that there exist systematic spectral changes below 2.5 eV even in the insulating state. In order to illustrate these changes clearly, we subtracted the contributions of the phonons and the $`p`$-$`d`$ transitions, indicated as a dot-dot-dashed line in Fig. 2(a), from each spectrum to obtain the contribution of the transitions between 4$`d`$ states, $`\sigma _{4d}(\omega )`$. Figure 2(b) shows the two-peak structure of $`\sigma _{4d}(\omega )`$. As $`T`$ decreases, the spectral weight of Peak $`\alpha `$ ($`S_\alpha `$) decreases, but that of Peak $`\beta `$ ($`S_\beta `$) increases. The sum of the spectral weights up to 3.0 eV remains the same, satisfying the optical sum rule. It should be noted that only Peak $`\alpha `$ shows the $`T`$-dependent peak shift.

To explain these spectral changes, we consider the 3 $`t_{2g}`$-orbital Hubbard model. When the orbital multiplicity is taken into account, the Hund’s rule exchange energy $`J`$ between $`t_{2g}`$ electrons should play an important role. The interactions among electrons on the same site can be described by $`U`$ Coulomb repulsion energy (CRE) between two electrons in the same orbital, $`U^{}`$ CRE between two electrons in different orbitals with opposite spins, and $`U^{\prime \prime }`$ CRE between electrons in different orbitals with the same spin. \[When the rotational symmetry in the orbital space is considered, $`U^{}`$= $`U2J`$, and $`U^{\prime \prime }`$= $`U3J`$ .\] As shown in Fig. 3, the energy cost of the $`d`$-$`d`$ transition (i.e., $`d^4`$ \+ $`d^4`$ $`d^3`$ \+ $`d^5`$) depends on the spin and the orbital configurations of the nearest neighboring Ru ions. For the time being, let us assume that all of the $`t_{2g}`$ states are degenerate. Then, we should consider four kinds of spin/orbital configurations. Figure 3(a), (b), (c), and (d) show possible $`d`$-$`d`$ transitions in FM (ferromagnetic)/FO, FM/AFO, AFM/FO, and AFM/AFO configurations, respectively. \[Here, FO (or AFO) implies that the same (or different) $`t_{2g}`$ orbitals are occupied in the two sites.\] With the above mentioned CRE’s, the corresponding energy costs of the $`d`$-$`d`$ transitions are estimated. As shown in Fig. 3, the FM/FO configuration does not allow any $`d`$-$`d`$ transition. And, the FM/AFO and the AFM/FO configurations allow only one transition. On the other hand, the AFM/AFO configuration allows two transitions with energy costs of $`UJ`$ and $`U+J`$ .

How can we understand the two-peak structure? Note that the Néel temperature $`T_N`$ of the x=0.06 sample is around 150 K . Near and below $`T_N`$, the nearest neighbor spin correlation is mostly AFM, so most excitations come from the AFM/AFO and the AFM/FO configurations. Then, Peaks $`\alpha `$ and $`\beta `$ can be assigned as excitations of $`UJ`$ and $`U+J`$, respectively. From the energy difference between two excitations, the value of $`2J`$ can be estimated to be about 1 eV. It is in good agreement with the earlier reports , thus demonstrating the validity of our peak assignments.

The $`T`$-dependent spectral weight changes in Fig. 2(b) can be understood as a result of changes of the AFO and the FO correlations. Using the Lorentzian fittings, we estimate $`S_\alpha `$ and $`S_\beta `$ . Since the value of $`S_\alpha `$ is similar to that of $`S_\beta `$ at most temperatures, the contribution of the AFO correlation seems to be more prevalent than that of the FO correlation. Figure 4 shows the $`T`$-dependent spectral weight changes of $`S_\alpha `$ and $`S_\beta `$. As $`T`$ decreases, $`S_\alpha `$ decreases, but $`S_\beta `$ increases. These $`T`$-dependences suggest that the FO correlation increases with decreasing $`T`$. Then, it can be said that there is a competition between AFO and FO configurations at least in the ground state of the x=0.06 sample.

Another interesting feature is that Peak $`\alpha `$ shifts to higher frequencies by about 0.24 eV with decreasing $`T`$, but Peak $`\beta `$ does not shift significantly. Note that $`U`$ and $`J`$ values for most solids have little $`T`$-dependences. To explain this intriguing behavior, we pay attention to the electron-phonon ($`el`$-$`ph`$) coupling. As $`T`$ decreases, it was known that the RuO6 octahedra rotate and become flattened . The inset of Fig. 2(b) shows the phonon spectra of the in-plane Ru-O stretching mode . As $`T`$ decreases, the phonon frequency $`\omega _{TO}`$ decreases rather significantly, which suggests an increase of the in-plane Ru-O bond length (i.e., the flattening of the octahedron). In addition, the strong $`el`$-$`ph`$ coupling makes the phonon lineshape asymmetric, in agreement with Raman measurements . Figure 4 also shows that the changes of $`\omega _{TO}`$ and $`\mathrm{\Delta }S_\alpha (T)`$ could be related.

Now, let us consider the $`el`$-$`ph`$ coupling energy $`E_{ph}`$. Note that the Ru ions with 4 $`t_{2g}`$ electrons cannot have degenerate $`t_{2g}`$ levels. Due to the strong Jahn-Teller-like distortion, the energy levels of the doubly and the singly occupied orbitals will change by -2$`E_{ph}`$ and $`E_{ph}`$, respectively . For example, let us consider the orbital polarized state, shown in Fig. 3(e), which is composed of two sites with doubly occupied $`d_{xy}`$ and $`d_{yz}`$ orbitals. Its schematic energy level with the Jahn-Teller-like distortion is shown in Fig. 3(f). Compared to the degenerate case, the orbital polarized state with the AFM/AFO configuration will have an additional energy cost of 3$`E_{ph}`$ in the $`UJ`$ excitation, so the position of Peak $`\alpha `$ should be located at $`UJ+3E_{ph}`$. However, the $`U+J`$ excitation contributing to Peak $`\beta `$ remains independent of the lattice distortion. With $`E_{ph}\omega _{TO}`$ $``$ 600 cm-1 ($``$ 0.074 eV), the shift of Peak $`\alpha `$ is estimated to be about 0.22 eV, in agreement with our experiment. The continuous shift of the $`UJ`$ excitation can be explained by the fact that short range orbital orderings, which accompanies the lattice distortion in Fig. 3(e), grows progressively. Near $`T_N`$, corresponding long range orbital orderings become stabilized and most of the spectral weights will move to $`UJ+3E_{ph}`$. Our work demonstrates that the $`el`$-$`ph`$ coupling should be strong in CSRO and play an important role in the evolution of the orbital degree of freedom. The shift of $`\omega _{TO}`$, due to the stong $`el`$-$`ph`$ coupling, should be closely related with the orthorhomic distortion. This distortion will suppress the AFO ordering  and can explain the close relation between $`\omega _{TO}`$ and $`\mathrm{\Delta }S_\alpha (T)`$, observed in Fig. 4.

To explain the electronic structure of the Ca2RuO4 Mott insulating state, Anisimov et al. proposed an FO ordered state of the $`d_{xy}`$ orbitals . This intriguing state can explain a Mott gap in the half-filled $`d_{yz/zx}`$ state and an orthorhombic lattice distortion. Recently, Hotta and Dagotto proposed another interesting AFO ordered state, stabilized by a combination of the correlation and the $`el`$-$`ph`$ coupling effects . In the AFO ordered state (shown in Fig. 1(e) of Ref. ), the two-dimensional network composed of $`d_{xy}`$ orbitals is occupied in a bipartite manner by half of the excess $`t_{2g}`$ electrons. The other excess electrons occupy $`d_{yz}`$ and $`d_{zx}`$ orbitals. The related lattice distortions should occur in pairs, resulting in a cooperative distortion in the total in-plane lattice. Our observation of the prevalence of the AFO correlation and the energy shift of the $`UJ`$ excitation seem to be consistent with the latter picture. However, the increase of the FO at lower $`T`$ cannot be simply explained.

One possible scenario is the phase coexistence of the FO and the AFO ordered states in the insulating CSRO. In the two-dimensional square network, the AFO ordered state will be preferred, since it provides the kinetic energy gain by allowing hoppings between the nearest neighbors . On the other hand, with the orthorhombic lattice distortion, the FO ordered state will be preferred . If the energy difference between two states is small, the FO and the AFO ordered Mott insulating states can coexist. Then, the insulating CSRO will be in an interesting state composed of two kinds of Mott insulators. Further works are required to verify this intriguing possibility.

In summary, we investigated the doping- and temperature-dependent optical conductivity spectra of Ca2-xSrxRuO4. Based on the 3-orbital Hubbard model, we could explain the two correlation-induced excitations. Moreover, from their spectral weight changes, we found that the electron-phonon coupling plays an important role in the dynamics of the spin/orbital correlations. We also proposed the possible phase coexistence of orbital ordered states in the insulating samples.

We would like to thank Y. Chung, J.-H. Park, Y. K. Bang, and T. Hotta for their help and discussions. We also acknowledge the Pohang Advanced Light Source for allowing us to use some of their facilities. This work was supported by the Ministry of Science and Technology through the Creative Research Initiative program and by KOSEF through the Center for Strongly Correlated Materials Research.


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# Designing molecules to bypass the singlet-triplet bottleneck in the electroluminescence of organic light-emitting-diode materials.

## I Introduction

Increased interest in the use of organic materialslevine  for a variety of optical and electronic applications, including the fabrication of electroluminescent devices, field-effect transistors, lasers etc., has followed the successful demonstration of devices with useful lifetimes and performance.tang87 ; jap95 ; at&t95 ; friend ; brown  The new advances depend on a better choice of organic materials, and on new technologies borrowed from recent developments in semiconductor technology, thin films, surface science and materials preparation. The luminescence of organic light emitting diodes (OLED) proceeds by the injection of electrons and holes which form excitons and then decay radiatively to the ground state.nilar  Although better design of the diode structure can improve the quantum efficiency of the device considerably, selection rules for optical transitions in these organic materials limit the radiative channel to singlet excitons. Hence the three-times more abundant triplet excitons decay by nonradiative channels and are wasted. This raises the possibility of an enormous gain in efficiency if the triplet excitons could also be harvested for light emission. Baldo et al. attempted to tap the triplet excitons by energy transfer from the host organic to a porphine-platinum flourescent dye.baldo

The objective of this work is to design the host material itself so that the singlet-triplet selection rules become irrelevant. This is done using heavy atoms where spin-orbit interactions ($`LS`$ coupling) become important, so that $`S^z`$ is no longer a good quantum number. We note in passing that the spin selection rules cannot be circumvented by applying magnetic fields, or incorporating local magnetic impurities since the spin remains a good quantum number even in the presence of such fields. It is necessary to bring the electrons into atomic sites where the spin-orbit coupling intervenes to break the spin selection rules. Since metal chelates (e.g., Al, In, Sc) of 8-hydroxyquinoline have provided some of the most successful OLED materials, we will consider molecules based on modifications of these standard materials.

## II New molecules

Since AlQ3, i.e., Al(8-hydorxyquinoline)3, has been a very successful host material (fig. 1) in OLEDS, we consider two structures derived from AlQ3 where the quinoline part is modified. These are shown in Figs. 2 and 3, and are obtained by first replacing the N atom by an As atom ( an arsenoquinoline, denoted by Al(AsQ)3 ), and then replacing the carbon atom para to the As atom by a boron atom, cf., fig. 3, to give Al(AsBQ)3. We proceed to investigate if such molecules are stable, and what luminescence properties could be expected from them, using sophisticated state of the art quantum chemical calculations. These molecules were chosen for this investigation following detailed studies of AlQ3 itself. For example, on examining the electron densities of the ground state and the excitonic states of AlQ3, it is found that the Al ion itself does not play a strong role in determining the exciton density. That is, replacing the Al by a heavy chelating atom where the $`LS`$ coupling is strong would not help the luminescence. This is also experimentally known to be true, e.g., in the Scandium complex. On the other hand, the N atom in the quinoline ring participates decisively in the relevant excitonic states. Thus replacing the N atom by As is appealing. Of course, the spin-orbit interaction is even stronger in Sb, but replacing N by Sb would be too strong a chemical modification and the synthesis of the corresponding molecule may be even more difficult. hence here we examine the case of replacing N by As. Preliminary calculations showed that the N$``$As substitution had the effect of shifting the luminescence to the red, while the shorter wavelength of the AlQ3 is more attractive for device applications. It was envisaged that replacing the p-C atom, i.e, the C atom in the para-position to the N-atom, by boron would shift the spectrum back to the shorter wavelength regime. In this communication we examine these questions using sophisticated quantum calculations. We find that the N$``$As leads to a strong improvement in the spectrum, without too much of an adverse red shift , while the further substitution of the p-C atom by B is not useful.

## III Results

The ground states of the metal chelates were calculated using the Gausssian-98 code at the B3LYP/3-21G\* level.gaus ; basis . Both Al(AsQ)3 and Al(AsBQ)3 were found to be stable. Hence it should be possible to achieve a synthesis of these materials. The vertical excitation spectra were calculated at the TDB3LYP/3-21G\* level.basis1 . At this point we have not included spin-orbit coupling as yet. This is because the chelate structures, containing three 8-hydroxyquinoline groups, are too large for a direct implementation of relativistic effects. This would be undertaken as the next stage of this investigation. In anticipation of those results we have simply replaced the triplet oscillator strengths which are zero by an analogous singlet oscillator strength and plotted the excitation spectra ( see also table I). Some justification for the assumption that the singlet $``$ groundstate oscillator strength and that for the triplet $``$ ground become very similar in the presence of the spin-orbit interaction in As is given in the appendix. The resulting enhanced triplet+singlet spectra as well as the standard (singlet only) spectra are shown in Fig. 4

The excitations marked with an asterisk in Table I, for AlQ3 and Al(AsQ)3 are transitions which involve the H (i.e., HOMO) and L (i.e, LUMO) orbitals in a major way. Thus in AlQ3, the first singlet, i.e., S1, is approximately 0.98H $``$ L + other configurations. while the T4 is approximately 0.96H $``$ L + other configurations. In the As substituted form Al(AsQ)3 we have T4 being 0.9H $``$ L + other configurations, while the S1 is higher in energy and is an admixture with 0.94H $``$ L + other configurations. Hence these transitions may be identified with the HOMO-LUMO gaps used in simplified theoretical schemes. Such simplified schemes are of course modified when CI is included, where in various excited states (based on the ground state determinant) get included. The deficiencies of the simpler schemes become quite evident when we go to the boron substituted form Al(AsBQ)3. Here it is not possible to identify a transition where the initial state is mostly HOMO (i.e., $`>`$ 90%). In fact, T5, at 2.105 eV has 0.9H but the final orbital is L+4 admixed with other configurations. The H $``$ L transitions are at T8 with 0.76H in the initial orbital, and S4 with 0.79H in the initial orbital. This shows that the B substitution effectively introduces transitions in the nominal H $``$ L gap of simplified theories. Four additional transitions of Al(AsBQ)3, which might be labeled T10, S7, S8, and S9 in the notation of Table I are at 2.908, 2.913, 3.057, and 3.103 eV and complete the same energy window as in the other two compounds.

Comparison of the calculate Al(Q)3 spectra with experiment is not shown here, since such a comparison was carried out in a previous publication.nilar  Such comparison require taking due account of solvent effects, or aggregation effects etc, and as well as considerations of non-radiative pathways, since the experimental spectral intensities are affected by many such factors. The objective of this study is to examine the Al(Q)3, Al(AsQ)3, and Al(AsBQ)3 spectra calculated under the same  conditions, and in the same energy window.

These results show the Al(AsQ)3 spectrum in the same energy window as Al(Q)3; however, its spectral features are more intense. The main intensity is red shifted by 0.3 eV, confirming the conclusions based on more elementary considerations. However, there are now transitions in the blue as well. The substitution of the p-carbon by boron, i.e, Al(AsBQ)3, shows that the stronger absorption lines are somewhat blue shifted. The center of gravity of the spectral intensity is slightly blue shifted, although many peaks in the middle of the energy range are red shifted. The substitution of a nominally trivalent boron atom for a nominally $`sp^2`$ C site leads to some distortion of the original ring structure. The improvement of the spectrum is questionable. Hence, it is clear that we need to look for a better choice than boron. In fact, Fig. 4 suggests that the Al(AsQ)3 provides an excellent improvement over the more usual AlQ3 while its synthesis would not be as difficult as the boron substituted form.

## IV conclusion

We show that the spectra of metal chelated 8-hydorxyquinolines can be manipulated and improved to obtain much better luminescence properties. We have shown how the spectrum can be shifted and that the intensity would increase if the triplet excitations could be harvested. The replacement of the N in AlQ3 by an As atom provides a definite improvement, while the further substitution of the p-Carbon by B is not seen to provide a useful improvement. This is a preliminary study which anticipates a more detailed calculation where the $`LS`$ coupling would be explicitly included.

*

## Appendix A  Some considerations of the spin-orbit interaction

The relativistic effects for heavy atoms can be included up to $`\alpha ^2`$, where $`\alpha `$ is the fine structure constant, in first principles pseudopotentials. The result splits into two terms of the form:

$$V_{rel}(r)=\underset{l}{}|l>[V_l(r)+V_l^{so}(r)𝐋.𝐒]<l|$$
(1)
where the $`l`$-sum is a sum over angular momentum states. The first term is the scalar part, and is not significant for the problem of the singlet-triplet bottleneck. The second term in the above equation, $`V_2=_l|l>V_l^{so}(r)𝐋.𝐒<l|`$ introduces mixing between orbital and spin angular momentum states, leading to the break down of the usual spin selection rules. However, the full inclusion of the spin-orbit term in first-principles CI calculations of the type discussed in this paper is numerically quite prohibitive, given the large number of electrons which need to be handled in typical LED materials. Leave aside CI calculations, the numerical evaluation even with a pseudopotential scheme is extremely demanding.joanno

The spin-orbit operator is highly local in the sense that it is mostly sensitive to changes in electron density close to the nucleus, where relativistic effects dominate. Thus we may look at calculations for systems containing As as a guide. In order to get at least a simple “grosso modo” estimate, we may compare the homo-lumo gap (bandgap) of As obtained from a non-relativistic (i.e, standard) calculation with a calculation where some effort is put into an evaluation of the relativistic effects.gonze  Thus Gonze et al. have carried out calculations which can be used for a simple estimate of the effect of the spin-orbit effect in As. The s-levels in As are about 9 eV lower than the p-levels. The p-levels suffer a splitting of about 0.36 eV in As, and is a measure of the strength of the spin-orbit term in As. Since we are concerned with singlet and triplet excitons, we should compare this spin-orbit splitting with the gap between hole energies and the Fermi energy, and electron energies and the Fermi energy in As. Numerical values for these, for As have been given by J.-P. Issi,issi , and by Priestly et al.,priestly . Issi gives 0.154 eV and 0.202 eV for electrons and holes, while Priestly et al give 0.177 and 0.190 eV. Hence the total effect for an electron-hole pair is of the order of 0.35 eV by one estimate, and 0.36 eV by the second estimate. These numbers are in fact very similar to the spin-orbit energy ($``$ 0. 36 eV). These considerations suggest that when estimating the oscillator strengths for the processes $`<eh(,)|\stackrel{}{r}|`$groundstate$`>`$ and $`<eh(,)|\stackrel{}{r}|`$groundstate$`>`$, we may, as a grosso modo estimate take the oscillator strengths to be of the same magnitude.

Fig.1 Structure of the light emitter AlQ3. See ref.structure  for bond lengths, angles etc.

Fig.2 N atoms of the quinolines have been replaced by As in Al(AsQ)3

Fig.3 The C atom in the para-position to N has been replaced by B in Al(AsBQ)3. The Kekule-type structure is only schematic.

Fig.4 Calculated spectra of the three compounds. Solid curves: only the singlet is available for light emission; dashed curves: the triplet exciton is also harvested (using a $`f_{os}`$ comparable to the nearest singlet (see appendix). Note that the intensity axis is logarithmic. The calculation is for isolated molecules, and hence a broadening of 0.025 eV has been included.