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# Density functional theory versus the Hartree Fock method: comparative assessment

## I Introduction

The Hartree-Fock method (HF) originate from the pioneer works of Hartree  and Fock . Since then an impressive progress has been achieved by using HF as a basis when calculating the ground state energy and constructing the Random Phase Approximation (RPA) and the Random Phase Approximation with Exchange (RPAE) to investigate the dynamic properties of multi-electron objects, such as atoms , molecules, clusters and fullerenes. Unfortunately, HF method has a number of difficulties in its application. For instance, one needs a whole set of single-particle wave functions to calculate the single-electron nonlocal potential. It is also necessary to follow a rather intricate procedure to include the correlation corrections that are beyond the HF framework. As a result, in the case of complex many-electron systems, starting with molecules, that include at least several atoms, the calculations become too complicated.

The Density Functional Theory (DFT) that was invented in the early 1960s has, generally speaking, overcome these difficulties. DFT has reduced the problem of calculating the ground state characteristics of a many-electron system in a local external field to the solution of the Hartree-like one-electron equations . At first DFT was limited to consideration of only the ground states of many-electron systems, leaving aside their dynamic properties, which are closely related to the systems behavior in the time-dependent external fields. This limitation of DFT was surmounted by Runge and Gross  by transforming DFT into the so-called Time-Dependent Density Functional Theory (TDDFT), which in fact is a quite natural generalization of DFT.

Both DFT and TDDFT are based on the one-to-one correspondence between the particle densities of the considered systems and external potentials acting upon these particles. For definiteness, we assume that the time dependent part of the considered electronic system’s density $`\rho (𝐫,t)`$, which is created under the action of an external time-dependent field $`\lambda v_{ext}(𝐫,t)`$, is developing from the system’s ground state. Consequently, one can conclude that the wave function and each observable, describing the system, can be presented as a functional of the density. Examples are the functionals of the ground state energy $`E[\rho ]`$ and of the action $`A[\rho ]`$ .

DFT and TDDFT establish an exact correspondence between a system of many interacting particles and a fictitious non-interacting Kohn-Sham (KS) system . The main advantage of this ”mapping” is that KS system is described by a set of Hartree-type single particle equations, which is not too difficult to solve. As a result, after solving these equations in the case of an external time-independent potential, one can obtain and predict, at least in principle, the atomic, molecular, cluster and solid bodies binding energies, phonon spectra, activation barriers etc. (see e.g. ). The same is true in the case of a time-dependent potential when the solution yields the single-particle and collective excitation spectra (see e.g. ).

Unfortunately, the one-to-one correspondence proved in  establishes the existence of the functionals only in principle, leaving aside a very important question on how one can construct them in reality. This is why the success of DFT and TDDFT strongly depends upon the availability of good approximations for the functionals. A systematic way to construct the required functionals and the corresponding response functions and effective interaction was suggested in a number of papers .

Since the HF and the Kohn-Sham theory play an important role in the many-body physics, it deserves comprehensive examinations in order to reveal their shortcomings and advantages as compared to one another when applied to studies of the many-electron systems. Recently, a key element of DFT, the action functional $`A[\rho ]`$, was suspected to be ill-defined because of a number of contradictions in it. It appeared that the contradiction, which came from the analysis of the causality and symmetry properties of the linear response functions in TDDFT, plays the central role in creating other contradictions . Fortunately, these contradictions were successfully resolved recently .

Exhaustive calculations of the ground state energies of different atoms within the HF approach and that based on the density functional corresponding to the HF approximation (DHF) have shown that there exists an inequality,

$$E_{DHF}E_{OEP}>E_{HF},$$
(1)
where $`E_{DHF}`$ is the ground state energy calculated in DHF, using a KS model system with the exact same density as that of some given HF ground states . Here $`E_{OEP}`$ denotes the energy from the optimized potential method (OPM) , and $`E_{HF}`$ denotes the HF ground state energy (see e.g. ). One can assume that inequality $`E_{OEP}>E_{HF}`$ results from the fact that $`E_{OEP}`$ is calculated with the restrictions associated with local potentials while calculations of $`E_{HF}`$ are in this sense unrestricted (see e.g. ). But such considerations could justify only the relation $`E_{OEP}E_{HF}`$. For instance, if one applies this consideration to the functional of the KS kinetic energy $`T_k[\rho ]`$ one would expect that $`T_k[\rho ]>T_k^{HF}[\rho ]`$. Quite surprisingly, one has instead $`T_k^{HF}[\rho ]T_k[\rho ]`$ ( see e.g. ). Here $`T_k^{HF}[\rho ]`$ is the HF functional of the kinetic energy. Then, one could expect, however, that instead the following relation holds (see, e.g. )

$$E_{DHF}=E_{OEP}=E_{HF},$$
(2)
since a universal Hohenberg-Kohn (HK) functional is defined for HF ground states because of the constrained-search derivation . Note, that this procedure also does not define explicitly the HF functional $`F^{HF}[\rho ]`$ whose minimization leads to the HF ground state. The obvious contradiction between inequality (1) and equality (2) casts doubts on the reliability of the KS scheme and probably points to the possible contradictions in DFT based on the suggestion that an exact local exchange potential does not exist for ground states of typical atoms (see  and references therein). To solve the problem, we have to clarify the relationships between the HF exchange and kinetic functionals and the corresponding exchange and kinetic functionals of the DFT.

Without resorting to a numerical analysis, by clarifying the relationship between the nonlocal exchange HF potential and the local exchange KS potential, we show that inequality (1) and equality (2) have to be replaced by the inequality

$$E_{OEP}E_{DHF}=E_{HF}.$$
(3)
We also consider the important problem of how to relate the single particle spectrum of a many electron system to the corresponding KS eigenvalues. This consideration enables us to clarify the relationship between the single particle spectra obtained in HF calculations and in the KS calculations.

The structure of the paper is the following. In Section II, for the reader’s convenience we review the main features of the HF method. We list only the main peculiarities of the HF method, which are directly determined by the nonlocal HF potential. One cannot expect to reproduce these within the Kohn-Sham theory of DFT. The explanation of Eqs. (1), (2), and (3) presented in Section III consists in demonstrating that the contradictions come from omitting the correlation energy, which is defined by the difference between the sum of the kinetic and exchange energies of a system considered within DFT and HF approaches, respectively. Consequently, this difference, which has to be treated as a correlation energy $`F_c^{HF}[\rho ]`$, gives rise to a specific correlation energy, because the nonlocal HF potential ensures the deeper minimum value of the ground state energy than the local potential of OPM. We also clarify the relationships between HF exchange and kinetic functionals and the corresponding exchange and kinetic functionals of the DFT. Our consideration also shows that this correlation energy $`F_c^{HF}[\rho ]`$, being the specific feature of a finite system, cannot be represented by the local density approximation based on calculations of a homogeneous electron system. Therefore, the correlation energy of a finite electron system, which has to include $`F_c^{HF}[\rho ]`$, cannot be obtained from considerations of uniform electron systems, although this way to construct $`E_c[\rho ]`$ is generally used . In Section IV, we consider the single-particle excitation spectra of many-electron systems and relate them to the eigenvalues of the corresponding KS equations. We show that the single-particle spectra do not coincide with the eigenvalues of the KS or HF equations. A possible inconsistency in the Kohn-Sham theory based on calculations of the single-particle spectra  is also clarified in this Section. Finally, Section V contains our concluding remarks.

## II The Hartree-Fock method

Hartree’s equations, as Fock’s generalization of them, were derived for any atom with two and more electrons. In fact, they are applicable to any many-electron system in a static external potential $`v(𝐫)`$. Assuming that the total electron wave function $`\mathrm{\Psi }(𝐫_1,\mathrm{}𝐫_N)`$ can be approximated as a product of one-particle functions $`\varphi _i^H(𝐫)`$, $`\mathrm{\Psi }^H(𝐫_1,\mathrm{}𝐫_N)=_{i=1}^N\varphi _i^H(𝐫_i),`$ Hartree suggested  the following equation for $`\varphi _i^H(𝐫)`$ Atomic system of units is used in this paper: $`e=m=\mathrm{}=1`$, where $`e`$ and $`m`$ are electron charge and mass, respectively.:

$$\left[\frac{\mathrm{\Delta }}{2}+v(𝐫)+\underset{j=1,ji}{\overset{N}{}}\frac{|\varphi _j^H(𝐫^{})|^2}{|𝐫𝐫^{}|}𝑑𝐫^{}\right]\varphi _i^H(𝐫)=E_i^H\varphi _i^H(𝐫).$$
(4)
Here $`N`$ is the total number of electrons. For an atom one has $`v(𝐫)=Z/r`$, where $`Z`$ is the nuclear charge. An electron in an $`i`$-state is under the action of the so-called self-consistent field, which is determined by all electrons but the $`i`$th one. Excluding the term $`j=i`$ from the sum in (4) eliminates the action of the $`i`$-electron upon itself. In Hartree approximation the system’s electron density $`\rho ^H(𝐫)`$ is determined by the relation

$$\rho ^H(𝐫)=\underset{j=1}{}n_i|\varphi _j^H(𝐫)|^2,$$

where $`n_i`$ are the occupation numbers.

Hartree’s approach has two obvious shortcomings: the total wave-function violates the exclusion principle and, since the self-consistent potential acting upon the $`i`$th electron depends upon $`i`$, the functions $`\varphi _i^H(𝐫)`$ are non-orthogonal. These shortcomings were eliminated in  by constructing the total wave function as an anti-symmetrized $`(A)`$ product,

$$\mathrm{\Psi }^{HF}(𝐫_1,\mathrm{}𝐫_N)=A\underset{j=1}{\overset{N}{}}\varphi _i^{HF}(𝐫_i),$$

which automatically satisfies the exclusion principle. This wave-function’s choice leads to the following ground state energy $`E_{HF}`$

$`E_{HF}`$ $`=`$ $`{\displaystyle \frac{1}{2}}{\displaystyle \underset{j=1}{}}n_j{\displaystyle \varphi _j^{}(𝐫)^2\varphi _j(𝐫)𝑑𝐫}+{\displaystyle \frac{1}{2}}{\displaystyle \underset{j=1,i=1}{}}n_jn_i{\displaystyle \frac{\varphi _j^{}(𝐫_1)\varphi _i^{}(𝐫_2)\varphi _j(𝐫_1)\varphi _i(𝐫_2)}{|𝐫_1𝐫_2|}𝑑𝐫_1𝑑𝐫_2}`$ (5)
$``$ $`{\displaystyle \frac{1}{2}}{\displaystyle \underset{j=1,i=1}{}}n_jn_i{\displaystyle \frac{\varphi _j^{}(𝐫_1)\varphi _i^{}(𝐫_2)\varphi _i(𝐫_1)\varphi _j(𝐫_2)}{|𝐫_1𝐫_2|}𝑑𝐫_1𝑑𝐫_2}+{\displaystyle \underset{j=1}{}}n_j{\displaystyle \varphi _j^{}(𝐫)\varphi _j(𝐫)v(𝐫)𝑑𝐫},`$ (6)
and HF system of equations:

$`\widehat{H}^{HF}\varphi _i^{HF}(𝐫)`$ $``$ $`\left[{\displaystyle \frac{\mathrm{\Delta }}{2}}+v(𝐫)\right]\varphi _i^{HF}(𝐫)`$ (7)
$`+`$ $`{\displaystyle \underset{j=1}{\overset{N}{}}}{\displaystyle \frac{d𝐫^{}}{|𝐫𝐫^{}|}\left[|\varphi _j^{HF}(𝐫^{})|^2\varphi _i^{HF}(𝐫)\varphi _j^{HF}(𝐫^{})\varphi _i^{HF}(𝐫^{})\varphi _j^{HF}(𝐫)\right]}=E_i^{HF}\varphi _i^{HF}(𝐫).`$ (8)
These equations differ from an ordinary Schrödinger equation in two essential aspects: they are non-linear in $`\varphi _i^{HF}(𝐫)`$ and the second term under the sum that represents the so-called Fock’s potential is non-local.

The non-linearity of Hartree and HF equations leads to non-uniqueness of their solutions (see  and references therein): in some cases, a given energy value can be represented by more than one set of solutions which deliver this value with high numerical accuracy. Furthermore, the nonlocal HF potential leads to a number of very specific features of the ground state wave function, which cannot be reproduced by the KS equations, see Sec. III.

1. The asymptotic behavior in $`r`$ of $`\varphi _i^{HF}(𝐫)`$, contrary to the case of an ordinary one-particle Schrödinger and also Hartree equations, is not determined by $`E_i^{HF}`$ and does not behave as

$$\varphi _i(𝐫)|_r\mathrm{}\mathrm{exp}(\sqrt{2|E_i^{HF}|}r).$$
(9)
On the contrary, it was shown in  that at $`r\mathrm{}`$ the function $`\varphi _i^{HF}(𝐫)`$ is not determined by $`E_i^{HF}`$ but is of the form

$$\varphi _i^{HF}(𝐫)|_r\mathrm{}_lC_l[\mathrm{exp}(\sqrt{2|E_F^{HF}|}r)]/r^{l+1},$$
(10)
where $`E_F^{HF}`$ is the energy of the so-called Fermi-level (with wave function $`\varphi _F^{HF}(𝐫)`$), which is the smallest binding energy among all $`E_i`$ in the considered system, and

$$C_l=\underset{m=l}{\overset{+l}{}}\varphi _F^{HF}(𝐫)r^l𝐘_{lm}(𝐫/r)\varphi _i^{HF}(𝐫)𝑑𝐫.$$
(11)
Here $`𝐘_{lm}(𝐫/r)`$ is the $`l^{th}`$ order spherical polynomial. The alteration of the asymptotic behavior dramatically affects, for example, the probability of penetration of atomic electrons via a potential barrier created when a strong electric static field is applied to this atom .

2. The number of zeroes in the radial part of the function $`\varphi _i^{HF}(𝐫)`$ is not equal, according to  and contrary to the case of an ordinary one-particle Schrödinger and also Hartree equations, to the so-called radial quantum number $`n_r=nl1`$, where $`n`$ is the principal and $`l`$ is the angular momentum quantum numbers. The extra zeroes are located at big distances and their presence can be explained qualitatively in the following way. At large distances $`\varphi _i^{HF}(𝐫)`$ is determined mainly by the admixture of $`\varphi _F^{HF}(𝐫)`$ to $`\varphi _i^{HF}(𝐫)`$. The latter function adds its remote zeroes to that of $`\varphi _i^H(𝐫)`$.

3. In the presence of the HF potential the electron velocity operator $`\widehat{𝐯}`$, which in quantum mechanics is determined by the relation $`\widehat{𝐯}=i[\widehat{H}^{HF},𝐫]`$, is not equal to $`\widehat{𝐩}`$ (note, that $`m=1`$), contrary to the case of a local potential. This drastically affects, for example, the photoionization cross section calculations: the amplitude of this process becomes different in the so-called length and velocity forms and the golden sum rule is violated . It is of interest to note that this violation is very serious and can be eliminated only when the corresponding calculations are performed within RPAE framework.

4. One-electron Green’s function $`G_E^{HF}(𝐫_1,𝐫_2)`$ in HF has only one expression via $`\varphi _i^{HF}(𝐫)`$, namely

$$G_E^{HF}(𝐫_1,𝐫_2)=\underset{i}{}\frac{\varphi _i^{HF}(𝐫_1)\varphi _i^{HF}(𝐫_2)}{E_iE+i\delta },$$
(12)
while in case of the spherical symmetry there exist two equivalent expressions for local potentials

$$G_E(r_1,r_2)=\underset{i}{}\frac{\varphi _i^{}(r_1)\varphi _i(r_2)}{E_iE+i\delta }=\varphi _E^{}(r_<)\chi _E(r_>),$$
(13)
where $`r_{>(<)}`$ is the larger (smaller) value of $`r_{1,2}`$ and $`\chi _E(r_>)`$ is the solution of the same Schrödinger (and also Hartree) equation as $`\varphi _E^{}(r_<)`$, but irregular at $`r=0`$. Note, that $`\varphi _E(r)`$ is regular at $`r0`$.

5. Another specific feature of the HF potential is the behavior as a function of the incoming electron energy $`E`$ of elastic scattering phase shifts $`\delta _l(E)`$ of a partial wave with angular momentum $`l`$. As is well known, if the wave function’s phase of electron scattering upon a local potential $`v(𝐫)`$ is normalized in such a way that $`\delta _l(E)|_E\mathrm{}0`$, the relation $`\delta _l(0)=q_l\pi `$ holds, where $`q_l`$ is the number of the electron’s vacant bound states with angular momentum $`l`$ in this potential (see e.g.). The situation for the HF potential is qualitatively different. With the same normalization $`\delta _l^{HF}(E)|_E\mathrm{}0`$ another relation holds: $`\delta _l^{HF}(0)=(q_l+t_l)\pi `$, where $`t_l`$ is the number of occupied bound states with angular momentum $`l`$ in the HF potential .

## III The KS local exchange potential and the Hartree-Fock nonlocal one

Consider a many-body system composed of $`N`$ interacting electrons and moving in an external potential $`v(𝐫)`$, with Hamiltonians $`\widehat{H}`$ and $`\widehat{H_v}`$ that are of the form

$$\widehat{H}=\widehat{T}+\widehat{U},$$
(14)
and

$$\widehat{H_v}=\widehat{T}+\widehat{U}+\widehat{V}.$$
(15)
Here $`\widehat{T}`$, $`\widehat{U}`$, and $`\widehat{V}`$ are given in terms of the field operators $`\widehat{\psi }(𝐫)`$, and $`\widehat{T}`$ is the kinetic energy operator

$$\widehat{T}=\frac{1}{2}\widehat{\psi }^{}(𝐫)^2\widehat{\psi }(𝐫)𝑑𝐫,$$
(16)
$`\widehat{U}`$ is the interelectron interaction energy operator

$$\widehat{U}=\frac{1}{2}\frac{\widehat{\psi }^{}(𝐫_1)\widehat{\psi }^{}(𝐫_2)\widehat{\psi }(𝐫_2)\widehat{\psi }(𝐫_1)}{|𝐫_1𝐫_2|}𝑑𝐫_1𝑑𝐫_2,$$
(17)
and $`\widehat{V}`$ is the potential energy operator in the field $`v(𝐫)`$

$$\widehat{V}=\widehat{\psi }^{}(𝐫)\widehat{\psi }(𝐫)v(𝐫)𝑑𝐫.$$
(18)
Hohenberg and Kohn proved that there exists a one-to-one correspondence between $`v(𝐫)`$ and the single-electron density $`\rho (𝐫)`$, that is $`v(𝐫)`$ is a unique functional of the density, apart from an additive constant . Because $`v(𝐫)`$ fixes the Hamiltonian Eq. (13), the ground state wave function $`\mathrm{\Psi }_0`$ is a functional of the density, and one can define the energy functional

$$E[\rho ]=F[\rho ]+v(𝐫)\rho (𝐫)𝑑𝐫,$$
(19)
with $`F[\rho ]`$ being a universal functional independent of the number of particles $`N`$ and the external potential $`v(𝐫)`$. Note that the functional $`F[\rho ]`$ can also be obtained on the basis of the constrained-search derivation of Levy, when it is defined by the minimum over the set of all normalized $`N`$-electron wave functions $`\mathrm{\Psi }_s`$ that determine the density $`\rho (𝐫)`$

$$F[\rho ]=\mathrm{min}\left(\mathrm{\Psi }_s|\widehat{T}+\widehat{U}|\mathrm{\Psi }_s\right).$$
(20)
Provided the density is exact, $`\rho (𝐫)=\rho _0(𝐫)`$, and normalized by the number of particles $`N`$, $`N=\rho (𝐫)𝑑𝐫`$, the functional $`E[\rho ]`$ assumes its minimum value that is equal to the ground state energy $`E_0`$

$$E_0=F[\rho _0]+v(𝐫)\rho _0(𝐫)𝑑𝐫.$$
(21)
Here the ground state density $`\rho _0(𝐫)`$ is determined by the equation

$$\frac{\delta F[\rho ]}{\delta \rho (𝐫)}+v(𝐫)=\mu ,$$
(22)
and $`\mu `$ is the so-called chemical potential. The number $`\mu `$ ensures the conservation of the number of particles $`N`$. It is clear that if $`\widehat{U}=0`$, \[see Eq. (13)\], the functional $`F[\rho ]`$ reduces to the functional $`T_k[\rho ]`$ of the kinetic energy of noninteracting particles.

Equation (20) can be replaced by a set of Hartree-like single-particle equations \[see Eq. (4)\], which permits the calculation of the density $`\rho (𝐫)`$

$$\left(\frac{}{2}+V_L(𝐫)\right)\varphi _i(𝐫)=\epsilon _i\varphi _i(𝐫),$$
(23)
with the potential $`V_L=V_H+V_{xc}+v`$. The density $`\rho (𝐫)`$ is given by

$$\rho (𝐫)=\underset{i}{}n_i|\varphi _i(𝐫)|^2.$$
(24)
Here $`V_H`$ is the Hartree potential \[see Eq. (4)\],

$$V_H(𝐫)=\frac{\delta }{\delta \rho (𝐫)}F_H=\frac{\rho (𝐫_1)}{|𝐫𝐫_1|}𝑑𝐫_1,$$
(25)
where $`F_H`$ is the Hartree functional

$$F_H=\frac{1}{2}\frac{\rho (𝐫_1)\rho (𝐫_2)}{|𝐫𝐫_1|}𝑑𝐫_1𝑑𝐫_2,$$
(26)
and the exchange-correlation potential, $`V_{xc}(𝐫)=\delta F_{xc}/\delta \rho (𝐫)`$, is obtained from the exchange-correlation functional,

$$F_{xc}[\rho ]=F[\rho ]T_k[\rho ]F_H[\rho ].$$
(27)
In the same way, it is possible to define separately $`F_x`$ and the correlation functional $`F_c`$ using the equation, which can be considered as a definition of $`F_c`$

$$F_c[\rho ]=F_{xc}[\rho ]F_x[\rho ].$$
(28)
Here $`F_x[\rho ]`$ is the exchange functional

$`F_x[\rho ]`$ $`=`$ $`{\displaystyle \frac{1}{2}}{\displaystyle \frac{\chi _0(𝐫_1,𝐫_2,iw)+2\pi \rho (𝐫_1)\delta (w)\delta (𝐫_1𝐫_2)}{|𝐫_1𝐫_2|}\frac{dw}{2\pi }𝑑𝐫_1𝑑𝐫_2}`$ (29)
$`=`$ $`{\displaystyle \underset{k,i}{}}n_kn_i{\displaystyle \left[\frac{\varphi _i^{}(𝐫_1)\varphi _i(𝐫_2)\varphi _k^{}(𝐫_2)\varphi _k(𝐫_1)}{|𝐫_1𝐫_2|}\right]𝑑𝐫_1𝑑𝐫_2},`$ (30)
and $`\chi _0`$ is the linear response function, which is of the form

$$\chi _0(𝐫_1,𝐫_2,\omega )=\underset{i,k}{}n_i(1n_k)\varphi _i^{}(𝐫_1)\varphi _i(𝐫_2)\varphi _k^{}(𝐫_2)\varphi _k(𝐫_1)\left[\frac{1}{\omega \omega _{ik}+i\eta }\frac{1}{\omega +\omega _{ik}i\eta }\right],$$
(31)
with $`\omega _{ik}`$ defined as $`\omega _{ik}=\epsilon _k\epsilon _i`$, $`\epsilon _k`$ and functions $`\varphi _k(𝐫_1)`$ being respectively the one-particle energies and wave functions of Eq. (21); $`\eta 0`$. Having the functional $`F_x`$ given by Eq. (27), we can construct the HF-like scheme based on Eq. (21) with the local KS exchange potential

$$V_x(𝐫)=\frac{\delta }{\delta \rho (𝐫)}F_x[\rho ].$$
(32)
The functional of density $`F_x^{KS}`$ corresponding to the HF approximation can be defined as follows

$$F_x^{KS}[\rho ]=T_k[\rho ]+F_H[\rho ]+F_x[\rho ].$$
(33)
In fact, this functional is determined by the value of $`F_x^{KS}[\rho ]=(\mathrm{\Phi }^{KS}|\widehat{H}|\mathrm{\Phi }^{KS})`$, if $`\mathrm{\Phi }^{KS}`$ is a single $`N`$-electron Slater determinant which delivers the lowest energy expectation value of $`\widehat{H}`$ given by Eq. (12) and yielding the density $`\rho (𝐫)`$. This determinant is composed of the single-particle wave functions, which are solutions of a single-particle equation like Eq. (21) provided that $`V_L(𝐫)`$ is a local potential. We denote this determinant by $`\mathrm{\Psi }^{KS}[\rho ]`$. On the other hand, the same wave function in the frame of the optimized effective potential  is determined by the local exchange potential $`V_{OPM}`$. Because of the one-to-one correspondence between this wave function and the local single-particle potential  we can conclude that $`V_{OPM}`$ coincides with $`V_x`$ given by Eq. (29). This result is in accord with the direct comparison of $`V_x`$ with $`V_{OPM}`$ that confirms their equality, $`V_x(𝐫)=V_{OPM}(𝐫)`$ . Therefore, the ground state energy $`E_{OEP}`$ of a many-electron system calculated in OPM has to be equal to the corresponding energy calculated with the functional given by Eq. (30), $`E_{KSX}`$, that is $`E_{KSX}=E_{OEP}`$.

Now we turn to the HF calculations based on the constrained-search formulation of DFT, which leads to the HF functional $`F^{HF}[\rho ]`$ . As it was mentioned in Section II and in accord with the constrained-search formulation , the HF functional is determined by the minimum of the expectation value $`F^{HF}[\rho ]=(\mathrm{\Psi }[\rho ]|\widehat{H}|\mathrm{\Psi }[\rho ])`$ when the minimization runs over all single-electron Slater determinants yielding the density $`\rho (𝐫)`$. The determinant, which yields the minimum value, is denoted as $`\mathrm{\Psi }_{HF}[\rho ]`$. This construction of the functional $`F^{HF}[\rho ]`$ makes it clear that the ground state energy $`E_{DHF}`$ of an electron system calculated with $`F^{HF}[\rho ]`$ is equal to $`E_{HF}`$. Note that the determinant $`\mathrm{\Psi }_{HF}[\rho ]`$ is composed of the eigenfunctions of Eq. (6) incorporating the Fock nonlocal potential. As a result, we can at first define the HF functional of the kinetic energy

$$T_k^{HF}[\rho ]=\left(\mathrm{\Psi }_{HF}[\rho ]|\widehat{T}|\mathrm{\Psi }_{HF}[\rho ]\right),$$
(34)
and then the HF functional of the exchange energy

$$F_x^{HF}[\rho ]=\left(\mathrm{\Psi }_{HF}[\rho ]|\widehat{U}|\mathrm{\Psi }_{HF}[\rho ]\right)F_H[\rho ].$$
(35)
We will now show that $`T_k^{HF}[\rho ]T_k[\rho ]`$, and our proof proceeds by reductio ad absurdum. Note that there is a one-to-one correspondence between $`\rho (𝐫)`$, the single-particle potential and the ground state wave function . Because $`T_k[\rho ]`$ is a unique functional of the density, each value of $`T_k[\rho ]`$ fixes the only ground state function. This function is a single Slater determinant $`\mathrm{\Phi }^{KS}`$ yielding the density $`\rho (𝐫)`$ normalized to $`N`$ electrons and characterized by the single-particle wave functions $`\varphi _i`$ and eigenvalues $`\epsilon _i`$, given by Eq. (21). Assume that $`T_k^{HF}[\rho ]=T_k[\rho ].`$ Then the HF wave functions $`\mathrm{\Psi }^{HF}[\rho ]`$ and the eigenvalues $`E_i^{HF}`$ given by Eq. (6) must be equal to $`\mathrm{\Phi }^{KS}[\rho ]`$ and the eigenvalues $`\epsilon _i`$ given by Eq. (21). As it was mentioned in Sec. II, Eq. (8), all of the HF single-particle functions have the same long-range behavior which is dominated by the smallest orbital energy , while, generally speaking, the eigenvalues $`E_i^{HF}`$ are not degenerate. On the other hand, eigenfunctions of Eq. (21) can have such a behavior only if the eigenvalues $`\epsilon _i`$ are degenerate. In order to eliminate the contradiction we have to recognize that $`T_k^{HF}[\rho ]T_k[\rho ]`$, and some of densities, which are the ground state densities of single-particle Schrödinger equations with nonlocal potentials are not noninteracting $`v`$ representable in the sense that they cannot be the ground state density of Eq. (21) with some local potential $`v(𝐫)`$. Note that examples of densities which are not $`v`$ representable were given in Ref. . Obviously, a one-to-one correspondence between nonlocal potentials and local ones does not exist . Therefore, if we would even have the functional $`F^{HF}[\rho ]`$ explicitly we would not have been able to calculate the HF ground state within the KS theory because the HF ground state cannot be reproduced by Eq. (21) with a local single-particle potential. On the other hand, the HF ground state can be obtained by solving the Hohenberg-Kohn equation (20) with $`F[\rho ]=F^{HF}[\rho ]`$. These facts do not imply any contradictions. The Kohn-Sham theory and Eq. (20) lead to the same result if the density $`\rho (𝐫)`$ of system under consideration is $`v`$ representable. Otherwise one has to use Eq. (20). A detailed investigation of this important problem will be published elsewhere.

The functional $`T_k^{HF}`$ given by Eq. (31) is determined in the domain of the HF densities $`\rho _{HF}`$ generated by the non-local Fock potential entering Eq. (6), while $`T_k`$ is determined in the domain of the densities $`\rho _L`$ given by Eq. (21). Note that both of the densities are normalized to same number of electrons. Approximating $`\rho _{HF}`$ by $`\rho _L`$, one has to obtain $`T_k<T_k^{HF}`$ because of the minimum principle which ensures that the Slater determinant $`\mathrm{\Phi }^{KS}`$ delivers the minimum value of the kinetic energy $`T_k`$. This result is confirmed by numerical calculations . On the other hand, due to the minimum principle $`F^{HF}<F_x^{KS}`$. Following Ref., we can define the HF exchange-correlation functional $`F_{xc}^{FH}[\rho ]`$

$$F_{xc}^{FH}=F_x^{HF}T_kF_H=T_k^{HF}+F_x^{HF}T_k,$$
(36)
and introduce the HF correlation functional $`F_c^{FH}`$

$$F_c^{FH}=F_{xc}^{FH}F_x=T_k^{HF}+F_x^{HF}T_kF_x.$$
(37)
We note that Eqs. (33) and (34) cannot be considered as exact definitions of $`F_{xc}^{FH}`$ and $`F_c^{FH}`$ because it is impossible to approximate exactly $`\rho _{HF}`$ by $`\rho _L`$. It follows from Eq. (34) that the correlation energy $`F_c^{HF}`$ exists. This energy must be taken into account when constructing constructing approximations of $`F^{HF}`$ within the KS framework. Omitting $`F_c^{HF}`$, one obtains Eq. (1), while properly constructing $`F^{HF}[\rho ]`$ based on the constrained-search formulation of DFT , one obtains Eq. (3) rather then Eq. (2).

In the case of He atoms the HF potential acting on the occupied states is a local potential. Therefore, the kinetic energy functional $`T_k^{HF}[\rho ]`$ coincides with $`T_k[\rho ]`$ leading to the equality $`F_x^{HF}[\rho ]=F_x^{KS}[\rho ]`$, and $`E_{OEP}=E_{DHF}=E_{HF}`$ in line with Eqs. (2) and (3). This observation is confirmed by numerical calculations . For all other atoms, the HF potential is nonlocal, and $`F_c^{HF}[\rho ]`$ contributes to the ground state energy. Obviously, one has $`E_{OEP}E_{DHF}=E_{HF}`$ in accordance with Eq. (3) and the numerical calculations . In the case of a homogeneous system, both single-particle wave functions, $`\varphi _i^{HF}(𝐫)`$ given by Eq. (6) and the ones $`\varphi _i(𝐫)`$ given by Eq. (21), are plane waves. As a result, the energy $`E_{KSX}=E_{HF}`$ (though the Fock potential, Eq. (6), is a nonlocal) and the correlation energy $`E_c=EE_{KSX}=EE_{HF}`$ is uniquely defined. This consideration shows that $`F_c^{HF}[\rho ]`$, being the specific feature of a finite system, cannot be approximated by the local density approximation based on calculations of a homogeneous electron system. Thus, $`E_c[\rho ]`$ of a finite electron system, which has to include $`F_c^{HF}[\rho ]`$, cannot be obtained from considerations of uniform electron systems, although this way to construct $`E_c[\rho ]`$ is generally used . As a result, we are led to the conclusion that the HF method has unique peculiarities which can be considered as useful rather then as shortcomings when investigating many-electron systems. Moreover, it is of great importance to check in experiments whether the wave function of a real physical system has the behavior resembling the behavior of the HF wave function given by Eq. (8) because this point is closely related to the problem of the $`v`$-representability. As mentioned in Sec. II, this HF-like behavior can be checked measuring the probability of penetration of atomic electrons via a potential barrier .

## IV  Single particle spectra

In order to calculate the single-particle energies $`ϵ_i`$ of a many-electron system we have to consider the ground state energy as a functional of the density $`\rho `$ and of the occupation numbers $`n_i`$. The occupation numbers are widely used in generalizations of DFT when extending DFT to finite temperatures, when considering excitations energies and so on, for a short review see Ref. . Taking into account $`n_i`$, we can use the well-known Landau equation of the Fermi liquid theory

$$\frac{\delta E}{\delta n_i}=ϵ_i.$$
(38)
We note that there exist close relations between the Fermi-liquid theory and DFT , while the Fermi-liquid theory is applicable in principle essentially to all types of Fermi systems including finite objects such as atoms, molecules, clusters and fullerenes. It is difficult to provide an example of a Fermi system, which cannot at all be described in the frame of this theory (see e.g. ).

In the functional $`E[\rho ,n_i]`$ both of the parameters, $`\rho `$ and $`n_i`$, are independent variables and determine different features of the system under consideration. The ground state energy as a functional of the density determines the system’s behavior in an external field, while the ground state energy as a functional of the occupation numbers characterizes the single-particle spectrum. On the other hand, the functional $`F[\rho ]`$ given by Eq. (18) depends only on the density. One can use some approximations to construct $`E[\rho ,n_i]`$. For instance, writing the density in explicit form given by Eq. (22), we find that the functional $`F[\rho ]`$ depends upon the occupation numbers $`n_i`$

$$F[\rho ,n_i]F\left[\underset{i}{}n_i|\varphi _i(𝐫)|^2\right],$$
(39)
while $`E[\rho ,n_i]`$ is given by Eq. (17). In that case, using Eq. (35) one can show that the single-particle energies $`ϵ_i`$ coincide with the eigenvalues $`\epsilon _i`$ of Eq. (21) .

Let us show that the procedure based on Eq. (36) may lead, however, to wrong results. Consider a large uniform system of fermions, so that it is possible to introduce the density of states at the Fermi-level. In this case, the single-particle potential is a constant, the eigenvalues of Eq. (21) are the eigenvalues of noninteracting fermions with bare mass $`M`$, and the density of states is equal to that of noninteracting fermions. This result is incorrect being related to the fact that the functional form $`E[\rho ,n_i]`$ given by Eq. (36) was artificially chosen. In contrast, as it is seen from Eq. (5), the HF ground state energy depends on the occupation numbers quite naturally and leads to the correct results when calculating the single-particle spectra . Inserting Eq. (5) into Eq. (35), we can calculate the HF single-particle spectrum $`ϵ_i^{HF}`$ that coincides with the eigenvalues of Eq. (6). In case of a large uniform system of electrons, one can check that the density of states tends to zero . Upon comparing this result with the result of the KS scheme, one may suspect an inconsistency in the KS approach. An inconsistency like this was indeed suspected in KS approach because $`_in_iϵ_i_in_iE_i^{HF}`$ , with $`ϵ_i`$ being calculated in the scheme of .

In order to show that the inconsistencies mentioned above are fictitious and to illustrate how to calculate the single-particle energies $`ϵ_i`$ within the DFT, we choose the simplest case when the functional is given by Eq. (30). As we shall see, the single-particle energies $`ϵ_i`$ coincide neither with the eigenvalues $`E_i^{HF}`$ of Eq. (6) nor with $`\epsilon _i`$ of Eq. (21). To proceed, we use a method developed in . The linear response functions $`\chi _0`$, and the density $`\rho (𝐫)`$ depend upon the occupation numbers. Thus, one can consider the ground state energy as a functional of the density and the occupation numbers

$$E[\rho (𝐫),n_i]=T_k[\rho (𝐫),n_i]+F_H[\rho (𝐫),n_i]+F_x[\rho (𝐫),n_i]+V_{ext}(𝐫)\rho (𝐫)𝑑𝐫.$$
(40)
Here $`T_k`$ is the functional of the kinetic energy of noninteracting KS particles. Substituting Eq. (37) into Eq. (35) and remembering that the single-particle wave functions and eigenvalues are given by Eq. (21), we see that the single particle spectrum $`ϵ_i`$ can be represented by the following expression:

$$ϵ_i=\epsilon _i<\varphi _i|V_x|\varphi _i>\frac{1}{2}\frac{\delta }{\delta n_i}\left[\frac{\chi _0(𝐫_1,𝐫_2,iw)+2\pi \rho (𝐫_1)\delta (w)\delta (𝐫_1𝐫_2)}{|𝐫_1𝐫_2|}\right]\frac{dwd𝐫_1d𝐫_2}{2\pi }.$$
(41)
The first and second terms on the right hand side in Eq. (38) are determined by the derivative of the functional $`T_k`$ with respect to the occupation numbers $`n_i`$. To calculate the derivative we consider an auxiliary system of non-interacting particles in a field $`U(𝐫)`$. The ground state energy $`E_0^U`$ of this system is given by the following equation

$$E_0^U=T_k+U(𝐫)\rho (𝐫)𝑑𝐫.$$
(42)
Varying $`E_0^U`$ with respect to the occupation numbers, one gets the desirable result

$$\epsilon _i=\frac{\delta E_0^U}{\delta n_i}=\frac{\delta T_k}{\delta n_i}+<\varphi _i|U|\varphi _i>,$$
(43)
provided $`U=V_H+V_x+v`$. The third term on the right hand side of Eq. (38) is related to the contribution coming from $`F_x`$ defined by Eq. (27). In the considered simplest case when we take into account only $`T_k`$, $`F_H`$ and $`F_x`$ functionals, the infraction enters as a linear factor, with $`F_H`$ and $`F_x`$ being linear dependent on the strength. If we omit the inter-electron interaction given by Eq. (15) we directly get from Eq. (37) $`ϵ_i=\epsilon _i`$ as it must be in the case of noninteracting system of electrons. Note that it is not difficult to include the correlation energy in the simplest local density approximation

$$F_c[\rho ,n_i]=\rho (𝐫)\epsilon _c(\rho (𝐫))𝑑𝐫.$$
(44)
Here the density $`\rho (𝐫)`$ is given by Eq. (22) and the correlation potential is defined as

$$V_c(𝐫)=\frac{\delta F_c[\rho ]}{\delta \rho (𝐫)}.$$
(45)
Then Eq. (37) takes the form

$$E[\rho (𝐫),n_i]=T_k[\rho (𝐫),n_i]+F_H[\rho (𝐫),n_i]+F_x[\rho (𝐫),n_i]+F_c[\rho (𝐫),n_i]+V_{ext}(𝐫)\rho (𝐫)𝑑𝐫.$$
(46)
Varying $`E[\rho (𝐫),n_i]`$ with respect to the occupation numbers $`n_i`$ and after some straightforward calculations, we obtain the rather simple expression for the single particle spectrum

$$ϵ_i=\epsilon _i<\varphi _i|V_x|\varphi _i>\underset{k}{}n_k\left[\frac{\varphi _i^{}(𝐫_1)\varphi _i(𝐫_2)\varphi _k^{}(𝐫_2)\varphi _k(𝐫_1)}{|𝐫_1𝐫_2|}\right]𝑑𝐫_1𝑑𝐫_2.$$
(47)
Here we employ Eq. (40) and choose the potential $`U`$ as $`U=V_H+V_x+V_c+v`$ to calculate the derivative $`\delta T_k/\delta n_i`$. Approximating the correlation functional $`F_c[\rho ,n_i]`$ by Eq. (41) we simplify the calculations a lot, preserving at the same time the asymptotic condition, $`(V_x+V_c)_r\mathrm{}1/r`$. This condition is of crucial importance when calculating the wave functions and eigenvalues of vacant states in the frame of the KS approach . Note, that these functions and eigenvalues that enter Eq. (44) determine the single particle spectrum $`ϵ_i`$. This spectrum has to be compared with the experimental results.

Single particle levels $`ϵ_i`$ given by Eq. (44) resemble the ones that are obtained using HF method. If the wave functions $`\varphi _i`$ were solutions of the HF equations, the correlation potential $`V_c`$ would be omitted, then the energies $`ϵ_i`$ would exactly coincide with the eigenvalues $`\epsilon _i`$. But this is not the case, since $`\varphi _i`$ and $`\epsilon _i`$ are the eigenfunctions and eigenvalues of Eq. (21). Therefore, the energies $`ϵ_i`$ coincide neither with HF eigenvalues given by Eq. (6), nor with the ones of Eq. (21). As we have seen in Section III, in case of the He atom $`T_k^{HF}[\rho ]=T_k[\rho ]`$ and $`F_x^{HF}[\rho ]=F_x^{KS}[\rho ]`$. Then it follows from Eq. (44) that $`_in_iϵ_i=_in_iE_i^{HF}=_in_i\epsilon _i`$ in accordance with numerical results obtained in . In case of other atoms we cannot expect this equality to hold because of the non-locality of the HF single-particle potential. This result is in agreement with the numerical calculations  and has nothing to do with contradictions between the HF method and DFT.

It is worth noting that if the exchange functional $`F_x[\rho ]`$ is treated within the local density approximation, as it is done for $`F_c[\rho ]`$, that is one uses Eq. (36) to construct $`E[\rho ,n_i]`$, then the second and the third terms on the right hand side of Eq. (44) cancel each other, leading to $`ϵ_i=\epsilon _i`$ in accordance with . Therefore it is of crucial importance to keep the proper representation of the functional $`F_x[\rho ]`$ given by Eq. (27). We also anticipate that Eq. (44) when applied to calculations of many-electron systems such as atoms and molecules will produce reasonable results for the energy gap separating the occupied and empty states. In case of solids, we expect that the energy gap at various high-symmetry points in the Brillouin zone of semiconductors and dielectrics can also be reproduced.

## V Concluding remarks

We have shown that there are no contradictions in DFT related to the fact that the HF-like calculations of finite electron systems carried out within the Kohn-Sham theory of DFT lead to the ground state energy, the absolute value of which is smaller than that calculated within the HF method. On the other hand, we have demonstrated that the properly constructed HF functional of the density produces the ground state energy, which coincides with the energy obtained within HF calculations. While inequalities (1) and (2) came from omitting the correlation energy, which is defined by the difference between the sum of the kinetic and exchange energies of a system considered within the KS approach and the HF method, respectively. It is the nonlocal exchange potential entering the HF equations that generates this correlation energy. We have shown that this functional $`F_c^{HF}`$ of the correlation energy, being the specific feature of a finite system, cannot be approximated by the local density approximation based on calculations of a homogeneous electron system. Thus, the correlation energy of a finite electron system, which has to include $`F_c^{HF}[\rho ]`$, cannot be obtained from considerations of uniform electron systems, although this way of constructing $`E_c[\rho ]`$ is generally used. We can conclude that the HF method has unique peculiarities which can be useful when investigating many-electron systems.

We have clarified the relationship between the eigenvalues of the single-particle KS equations, the HF eigenvalues and the real single-particle spectrum. Again, there are no contradictions based on the comparison of the single-particle spectra calculated within DFT and the HF method. We have presented a simple equation defining the single-particle spectrum of a many-electron system. It is worth noting that all the specific features of the HF method mentioned in Section II are dictated by the HF nonlocal potential and therefore give no grounds to seek possible contradictions in the Kohn-Sham theory which deals with local single-particle potentials and $`v`$ representable densities. As it was mentioned in Section II, the HF method has some drawbacks. Among them there is a well-known consequence of the non-locality of the HF single-particle exchange potential, which leads to the fact that the HF single-particle potential acting on the unoccupied states falls of exponentially. As a result, the HF potential can support very few unoccupied states. Such a poor situation with the number of states develops difficulties in treating the excited states. By contrast, the KS theory does not suffer from the drawbacks of the HF method.

## VI Acknowledgments

The visit of VRS to Clark Atlanta University has been supported by NSF through a grant to CTSPS. MYaA is grateful to the S.A. Shonbrunn Research Fund for support of his research. AZM is supported by US DOE, Division of Chemical Sciences, Office of Basic Energy Sciences, Office of Energy Research. This work was supported in part by the Russian Foundation for Basic Research, project no. 01-02-17189.


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# Split Clifford modules over a Hilbert space

## 1. Introduction

Let $`Z`$ be a real separable prehilbert space and $`C(Z)`$ the corresponding Clifford Algebra, i.e., the quotient of the Tensor Algebra of $`Z`$ by the ideal generated by the elements of the form $`z_1z_2+z_2z_1+2(z_1,z_2)1`$, with $`z_1,z_2Z`$. We determine here all the representations of $`C(Z)`$ on real separable Hilbert spaces where the elements of $`ZC(Z)`$ act skew-adjointly. Equivalently, all sequences $`J_1,J_2,\mathrm{}`$ of orthogonal, mutually anticommuting complex structures on a real Hilbert space.

Without loss of generality we may assume that $`Z`$ is complete as well. Every such representation gives rise, upon complexification, to a representation of the algebra $`C_{}(Z)=C(Z)`$ on a complex Hilbert space, whith $`Z`$ acting by skew-hermitian operators. A complete set of representatives of such representations up to equivalence was given by Gårding and Wightman \[GW\].

In this article we determine which Gårding-Wightman modules split over $``$ and describe all their $`C(Z)`$-invariant real forms up to equivalence. These effectively solves the problem, since any $`C(Z)`$-module must arise as one of these invariant forms.

To put the results in perspective, recall that for $`m=dimZ<\mathrm{}`$, the question of when a given $`C_{}(^m)`$-module, or space of spinors, splits over $``$, goes back to E. Cartan and Killing \[C\], who also provided the answer and geometric interpretation. The representations of $`C_{}(^m)`$ are direct sums of either one or two finite dimensional irreducible representations, depending on whether $`m`$ is even or odd. These remain irreducible over $``$ if $`m1,2,`$ mod. (4) and split into a direct sum two dual irreducibles otherwise. In particular, a $`C_{}(^m)`$-module splits over $``$ if and only if $`m0,3`$ mod.(4). We recover this result, at least when $`m`$ is even.

If $`dimZ=\mathrm{}`$ the situation is much more complicated, as can be expected. Rather, the remarkable feature of the infinite Clifford Algebra -as well as its bosonic cousin, the Heisenberg Lie Algebra, is that its representations can be parametrized at all and the possible real forms described. In \[GW\], the resulting set is described as “a true maze”. Since both there and here the matters of equivalence and irreducibility are not completely settled, an alternative argument is required to analize the splitting problem in infinite dimensions. In any case, although Clifford and Heisenberg Algebras are exceptions to Kirillov’s dictum that “in infinite dimensions there are no theorems, only examples”, it is the examples what may matter most.

The basic Fermi-Fock representations, familiar to physicists, do not split and in fact are irreducible over $``$. But we find others that are irreducible over $``$, split over $``$ and the corresponding factors are essentially new, i.e., they do not arise by restriction of any $`C_{}(Z)`$-module.

Although the examples of the latter kind may fail as models for quantum fields because they lack a vacuum (or only apply to systems with infinite energy), they do have natural realizations in $`L_2(𝕋)`$ which are closely related to wavelets and multilinear operators. The Clifford Algebra acts by singular integral transforms on the circle and the corresponding splittings can be interpreted in terms of wavelets. Conversely, this picture describes wavelets as infinite-dimensional spinors.

We are grateful to H. Araki, A. Grunbaum, A. Jaffee, V. Kac and J. Vargas for their useful advise.

## 2. The Gårding-Wightman modules

We describe here the results of \[GW\] and translate them in the language of Clifford modules (see also \[G\], \[BSZ\]). According to \[GW\], a representation of the Canonical Anticommutation Relations (CAR) consists of a countable set of bounded linear operators $`a_k`$ acting on a separable complex Hilbert space $`H`$, satisfying

$$a_ja_k+a_ka_j=0a_ja_k^{}+a_k^{}a_j=\delta _{jk}.$$

The $`a_k`$ and $`a_k^{}`$ are sometimes called the (fermionic) creation and anihilation operators, respectively.

To view these as representations of $`C_{}(Z)`$, we choose a complex structure $`\sigma `$ on $`Z`$ compatible with its metric, making $`(Z,\sigma )`$ into a complex-hermitian Hilbert space and a unitary basis $`z_1,z_2,\mathrm{}`$ of it, so that $`\{z_k,\sigma (z_k)\},`$ is a real orthonormal basis of $`Z`$. Then, the following formulas define a 1-1 correspondence between representations of the CAR and continuous representations $`𝕁`$ of the algebra $`C_{}(Z)`$ on $`H`$ such that the operators $`𝕁_z`$, $`zZ`$, are skew-hermitian:

$$a_k=\frac{1}{2}\left(𝕁_{\sigma (z_k)}+i𝕁_{z_k}\right)a_k^{}=\frac{1}{2}\left(𝕁_{\sigma (z_k)}+i𝕁_{z_k}\right).$$
$`2.1`$
Note that $`z𝕁_z`$ is not assumed to be $``$-linear and that for $`zZ`$, $`|z|=1`$, the operator $`𝕁_z`$ is unitary and its square is $`I`$.

Let $`X`$ be the set of sequences $`x=(x_1,x_2,\mathrm{})`$ where each $`x_i`$ is $`0`$ or $`1`$ (space of fermionic “occupation numbers”). $`X`$ is a group under componentwise addition modulo $`2`$. Let $`\mathrm{\Delta }`$ be the subgroup of $`X`$ consisting of sequences with only finitely many $`1`$’s. It is generated by the sequences $`\delta _k`$ where the $`k`$-th component is $`1`$ and the all others are $`0`$. The Gårding-Wightman (or GW) modules are parametrized by triples

$$(\mu ,\nu ,\{c_k\})$$
$`2.2`$
with the following objects as entries:

$`\mu `$ is a positive measure over the $`\sigma `$-algebra generated by the sets $`X_k=\{xx_k=1\}`$, which is quasi-invariant under translations by $`\mathrm{\Delta }`$. This means that its translates $`\mu _\delta (E)=\mu (E+\delta ),`$ $`\delta \mathrm{\Delta }`$, all have the same sets of measure zero and implies the existence of the Radon-Nikodym derivatives $`d\mu _\delta /d\mu `$.

$`\nu :X_+\{\mathrm{}\}`$ is a measurable function such that $`\nu (x+\delta )=\nu (x)`$ for all $`\delta \mathrm{\Delta }`$ and almost all $`xX`$.

$`c_k(x):H_xH_{x+\delta _k}H_x`$ is a sequence of unitary operators depending measurably on $`x`$ and satisfying

$`c_k^{}(x)`$ $`=c_k(x+\delta _k)`$ $`2.3`$
$`c_k(x)c_l(x+\delta _k)`$ $`=c_l(x)c_k(x+\delta _l)`$
The Hilbert space isomorphisms $`H_{x+\delta _k}H_x`$ are part of the data, although changing them results in unitarely equivalent representations. One may therefore assume that the family $`H_x`$ is invariant under translations by $`\mathrm{\Delta }`$.

The representation associated to a triple $`(\mu ,\nu ,\{c_k\})`$ is realized in the Hilbert space

$$H=_X^{}H_x𝑑\mu (x)$$
$`2.4`$
and defined by the following formulae, where an $`fH`$ is regarded as an assignement $`xf(x)H_x`$:

$`(𝕁_{z_k}f)(x)`$ $`=(1)^{x_1+\mathrm{}+x_{k1}+1}ic_k(x)\sqrt{{\displaystyle \frac{d\mu (x+\delta _k)}{d\mu (x)}}}f(x+\delta _k)`$ $`2.5`$
$`(𝕁_{\sigma (z_k)}f)(x)`$ $`=(1)^{x_k}i(𝕁_{z_k}f)(x)`$
The main observation here is that in any representation of the CAR, the operators $`N_k=a_k^{}a_k`$ and $`N_k^{}=a_ka_k^{}`$ form a conmuting set of projections over the sets $`X_k`$ and their complements $`X_k^{}`$, respectively, so that

$$(N_kf)(x)=x_kf(x)(N_k^{}f)(x)=(1x_k)f(x)$$
$`2.6`$
for all $`fH`$ and for almost all $`x`$. The direct integral (2.4) is just the corresponding spectral decomposition.

Setting

$$A_k=i𝕁_{z_k}B_k=i𝕁_{\sigma (z_k)},$$

our notation becomes consistent with that of \[GW\].

## 3. Real Clifford modules

If $`V`$ is a (real) module over $`C(Z)`$, then $`V`$ is a (complex) module over $`C(Z)`$ with the $`C(Z)`$-invariant decomposition over $``$

$$V=ViV;$$

$`V`$ is an invariant real form of $`V`$. Hence, to determine all real modules over $`C(Z)`$ it is enough to determine all the invariant real forms of the Gårding-Wightman modules. This is equivalent to determining all the antilinear operators $`S:HH`$ (the corresponding complex-conjugations) which commute with $`C(Z)`$ and such that

$$S^2=1,Sf=f.$$
$`3.1`$
As $`S`$ is a $`C(Z)`$-morphism and $`A_k=i𝕁_{z_k}`$ and $`B_k=i𝕁_{\sigma (z_k)}`$ by (2.1) and (2.5), we know that for all $`k`$

$$SA_k=A_kS\text{and}SB_k=B_kS.$$
$`3.2`$
Hence,

$$SN_k=N_k^{}S.$$
$`3.3`$
Every operator $`L`$ that conmutes with $`N_k`$ and $`N_k^{}`$ for all $`k`$ is an operator of multiplication by an essentially bounded measurable operator-valued function $`\varphi `$:

$$(Lf)(x)=(L_\varphi f)(x)=\varphi (x)f(x)$$

(cf. \[G\] ). In particular, $`N_k`$ and $`N_k^{}`$ correspond to multiplication by the characteristic functions of the sets $`X_k`$ and $`X_k^{}`$ respectively (see (2.6)).

From now on, we let $`H`$ be the complex Clifford module associated to $`(\mu ,\nu ,c_k)`$ as in the previous section.

###### Lemma 3.4

Suppose that $`H`$ admits an invariant real structure $`S`$. Let $`EX`$ be measurable and $`\chi _E`$ its characteristic function. Then, if

$$\mathrm{𝟙}E=\{\mathrm{𝟙}x=(1x_1,1x_2,\mathrm{})xE\},$$

(i) $`SL_{\chi _E}=L_{\chi _{\mathrm{𝟙}E}}S`$.

(ii) $`\mathrm{Supp}(Sf)=\mathrm{𝟙}\mathrm{Supp}(f)`$.

(iii) $`(Sf,Sg)=\overline{(f,g)}`$.

###### Demonstration Proof

$`(i)`$ follows from (3.3) and the fact that $`X_k`$ and $`X_k^{}`$ generate the $`\sigma `$-algebra where $`\mu `$ is defined. To prove $`(ii)`$, set $`F=\mathrm{Supp}(f)`$. Then

$$\mathrm{Supp}(Sf)=\mathrm{Supp}(S\chi _Ff)=\mathrm{Supp}(\chi _{\mathrm{𝟙}F}Sf)\mathrm{𝟙}F.$$

As $`S`$ is an involution,

$$F=\mathrm{Supp}(S^2f)\mathrm{𝟙}\mathrm{Supp}(Sf)\mathrm{𝟙}(\mathrm{𝟙}F)=F.$$

Consequently, all these inclusions are equalities and the assertion follows. For $`(iii)`$, as $`S`$ preserves norm, $`\mathrm{R}e(Sf,Sg)=\mathrm{R}e(f,g)`$. Also,

$$\mathrm{I}m(Sf,Sg)=\mathrm{R}e(iSf,Sg)=\mathrm{R}e(Sif,Sg)=\mathrm{R}e(if,g)=\mathrm{I}m(f,g),$$

finishing the proof. ∎

If $`\mu `$ is a measure on $`X`$, then

$$\stackrel{~}{\mu }(E)=\mu (\mathrm{𝟙}E)$$

is another.

###### Theorem 3.5

$`H`$ admits an invariant real form if and only if $`\mu `$ and $`\stackrel{~}{\mu }`$ are equivalent, $`\nu (x)=\nu (\mathrm{𝟙}x)`$ for almost all $`xX`$ and there exist a measurable family of operators

$$r(x)H_xH_{\mathrm{𝟙}x}H_x$$

which are antilinear, preserve the norm and satisfy

$$r(x)r(\mathrm{𝟙}x)=1,r(x)c_k(\mathrm{𝟙}x)=(1)^kc_k(x)r(x+\delta _k)$$
$`3.6`$
for all $`k`$ and almost all $`xX`$.

###### Demonstration Proof

Assume that $`S`$ is an invariant real structure on $`H`$. To see that $`\mu `$ and $`\stackrel{~}{\mu }`$ are equivalent, it is enough to prove that $`\stackrel{~}{\mu }(E)>0`$ whenever $`EX`$ is measurable and $`\mu (E)>0`$. To this end, write $`X=_{n>1}E_n`$ where $`E_n=\{x\nu (x)=n\}`$. We can assume that $`EE_n`$ for some $`n`$. Let $`h`$ be a unit vector of $`H_x`$ for some $`xE`$. Define the functions $`f(x)=\chi _E(x)h`$ and $`g(x)=(Sf)(x)`$. As $`S`$ preserves norms

$$\mu (E)=f=Sf=g$$

By the Lemma 3.4, the support of $`g`$ is $`\mathrm{𝟙}E`$, so

$`\mu (E)`$ $`=\left({\displaystyle _{\mathrm{𝟙}E}}(g(x),g(x))𝑑\mu (x)\right)^{\frac{1}{2}}`$
$`=\left({\displaystyle _E}(g(\mathrm{𝟙}x),g(\mathrm{𝟙}x))𝑑\stackrel{~}{\mu }(x)\right)^{\frac{1}{2}}`$
Then, $`\stackrel{~}{\mu }(E)=0`$ implies $`\mu (E)=0`$, which is a contradiction.

To see that $`\nu (x)=\nu (\mathrm{𝟙}x)`$ for almost all $`xX`$, assume the contrary. Then for some $`n`$ there exists a set $`EE_n`$ such that $`\mu (E)>0`$ and $`\mathrm{𝟙}EE_{n1}`$. Let $`\{h_i\}_{i=1}^n`$ be an orthonormal basis of the $`n`$-dimensional Hilbert space $`H_n`$ ($`H_xH_n`$ for all $`xE`$). Set $`f_i(x)=\chi _E(x)h_i`$ and $`g_i=Sf_i`$ for $`i=1,\mathrm{},n`$. We will prove that for almost all $`x`$, $`\{g_1(x),\mathrm{},g_n(x)\}`$ are $`n`$ non-zero orthogonal vectors in $`H_{\mathrm{𝟙}x}`$, is a contradiction, since we have assumed $`\mathrm{𝟙}EE_{n1}`$.

For an arbitrary $`FE`$ with $`\mu (F)>0`$, we have that

$`0L_{\chi _F}f_i^2`$ $`=SL_{\chi _F}f_i^2=L_{\chi _{\mathrm{𝟙}F}}Sf_i^2`$
$`={\displaystyle _X}\chi _{\mathrm{𝟙}F}(x)g_i(x)^2𝑑\mu (x)`$
$`={\displaystyle _{\mathrm{𝟙}F}}g_i(x)^2𝑑\mu (x)`$
Since $`F`$ is arbitrary and $`\mu `$ and $`\stackrel{~}{\mu }`$ are equivalent we have that $`g_i(x)0`$ a.e., and hence $`g_i(x)0`$ a.e.

We now prove that $`\nu (x)=\nu (\mathrm{𝟙}x)`$ almost everywhere. If not, there would be a set of positive measure $`E`$ such that $`EE_n`$ and $`\mathrm{𝟙}EE_{n1}`$, for some $`n`$. Since $`\mu `$ and $`\stackrel{~}{\mu }`$ are equivalent, $`\mu (\mathrm{𝟙}E)>0`$. Since $`\{f_i\}_{i=1}^n`$ is an orthogonal set in $`H`$, so is $`\{L_{\chi _F}f_i\}_{i=1}^n`$ for any given subset $`FE`$. By Lemma (3.1), the elements $`SL_{\chi _F}f_i=L_{\chi _{\mathrm{𝟙}F}}g_i`$ are also orthogonal. Therefore, for all $`ij`$

$$_{\mathrm{𝟙}F}(g_i(x),g_j(x))𝑑\mu (x)=0.$$

Since $`\mu \stackrel{~}{\mu }`$ and $`F`$ is arbitrary, we conclude that for almost all $`x\mathrm{𝟙}E`$, $`(g_i(x),g_j(x))=0.`$ On the other hand, $`\stackrel{~}{\mu }(F)=_{\mathrm{𝟙}F}g_j(x)^2𝑑\mu (x)`$ for almost all $`x\mathrm{𝟙}F`$. Therefore $`g_j0`$, so that the $`g_j`$ cannot vanish. Since $`E`$ has dimension $`n1`$, this is a contradiction. We conclude that $`\nu (x)=\nu (1x)`$ for almost all $`x`$.

Up to identifications, we may now assume that $`H_x=H_{\mathrm{𝟙}x}`$. Define the operator $`T:HH`$ by

$$(Tf)(x)=\sqrt{\frac{d\stackrel{~}{\mu }(x)}{d\mu (x)}}f(\mathrm{𝟙}x)$$

$`T`$ is $``$-linear, unitary and satisfies the relations

$$T^2=1TN_k=N_k^{}T$$

The product $`ST`$ is then an antilinear operator on $`H`$ which conmutes with all the $`N_k`$ and $`N_k^{}`$. Therefore it can be represented as multiplication by a measurable operator-valued function $`r(x)`$,

$$(STf)(x)=r(x)f(x)$$

where $`r(x):H_xH_x=H_{1x}`$ is antilinear and preserves norm. Since $`T`$ and $`S`$ are involutions, we obtain, respectively,

$$(Sf)(x)=r(x)(Tf)(x)=r(x)\sqrt{\frac{d\stackrel{~}{\mu }(x)}{d\mu (x)}}f(\mathrm{𝟙}x).$$

and

$$r(x)r(\mathrm{𝟙}x)=1.$$

$`S`$ anticommutes with the operators $`A_k`$ and $`B_k`$, because it commutes with $`𝕁`$. Therefore

$$r(x)(1)^{x_1+\mathrm{}+x_{k1}+k1}c_k(\mathrm{𝟙}x)=(1)^{x_1+\mathrm{}+x_{k1}+1}c_k(x)r(x+\delta _k)$$

and $`r(x)c_k(\mathrm{𝟙}x)=(1)^kc_k(x)r(x+\delta _k)`$ follows.

Conversely, if $`\mu `$ and $`\stackrel{~}{\mu }`$ are equivalent, $`\nu (x)=\nu (\mathrm{𝟙}x)`$ a.e. and there exist antilinear operators $`r(x)H_xH_x`$ that preserve norm and satisfy (3.6) a.e., we can define $`T`$ and $`S`$ as above. Is straightforward to see that $`S`$ is in fact an invariant real form of $`H`$. ∎

If $`dimZ=2m<\mathrm{}`$, $`\mu `$ and $`\stackrel{~}{\mu }`$ are equivalent because they are quasi-invariant discrete measures concentrated in the same coset of $`\mathrm{\Delta }`$ (namely, $`X=\mathrm{\Delta }`$ itself) \[GW\]. From (3.5) we deduce

$$r(\mathrm{𝟙})=(1)^{\frac{m(m+1)}{2}}r(\mathrm{𝟘}).$$

Assuming, as we may, that $`r(\mathrm{𝟘})`$ is the standard conjugation on $``$, we see that $`H`$ splits $`/`$ if and only if $`m(m+1)/2`$ is an even integer, that is, for $`m0,3`$ modulo $`4`$, as is well known.

In the infinite-dimensional case there are always plenty of solutions $`r(x)`$ to the equations (3.6). They can all be described by fixing a full set $`AX`$ of representatives of $`X`$ modulo $`\mathrm{\Delta }(\mathrm{\Delta }+1)`$, defining $`r(a)`$ on $`A`$ arbitrarely and extending it to all of $`X`$ according to the rules

$$r(\mathrm{𝟙}a)=r(a)^1,r(x+\delta _k)=(1)^kc_k(x)^1r(x)c_k(\mathrm{𝟙}x).$$

In this sense, any GW module with $`\nu `$ invariant and $`\mu `$ quasi-invariant under translation by $`1`$, “splits over $``$”. But since the set $`A`$ is not measurable, the resulting operators $`r(x)`$ may not be either. The difficulty of deciding whether a given GW module actually splits, i.e., whether there is a measurable $`r(x)`$, depends on the module, as we see next. Assume now that $`Z`$ is infinite dimensional and separable.

###### Corollary 3.7

If $`\mu `$ is discrete and $`H`$ is irreducible over $``$, then it is irreducible over $``$. In particular, this is the case for the Fermi-Fock representation.

###### Demonstration Proof

A proper invariant real subspace $`UH`$ must be a real form of $`H`$. Indeed, $`UiU`$ is complex, invariant and proper, hence equal to $`\{0\}`$ by irreducibility. By the same reason, $`UiU`$ is complex, invariant and not $`\{0\}`$, hence equal to $`H`$. Since the measure $`\mu `$ is discrete and $`H`$ is irreducible, $`\mu `$ is concentrated in some translate $`x_o+\mathrm{\Delta }`$, $`x_oX`$ \[GW\]. As $`X`$ is infinite, $`\mathrm{𝟙}(x_o+\mathrm{\Delta })`$ and $`x_o+\mathrm{\Delta }`$ are disjoint. This implies that $`\mu `$ and $`\stackrel{~}{\mu }`$ are not equivalent and therefore $`H`$ cannot have an invariant real form.

The Fermi-Fock representation corresponds to the triple $`(\mu ,1,1)`$, where $`\mu (\delta _k)=1`$ for all $`k`$ and $`\mu (X\mathrm{\Delta })=0`$, hence it is supported in the discrete set $`\mathrm{\Delta }`$. ∎

###### Corollary 3.8

Let $`\mu _X`$ be the Haar measure on $`X`$. Then the representation associated to the triple $`(\mu _X,1,1)`$ is irreducible over $``$.

###### Demonstration Proof

Irreducibility over $``$ follows from the ergodicity of the Haar measure, as argued in \[GW\]. Irreducibility over $``$ follows from Theorem 4 in \[G\], which implies that any function $`r(x)`$ satisfying

$$r(x+\delta _k)=(1)^kr(x)$$

must be non-measurable. ∎

While determining if a GW module has an invariant real form may not always be easy, it is still possible to obtain all the real $`C(H)`$ modules up to orthogonal equivalence. The next and final Theorem shows that any pair consisting of a GW module together with an invariant real form, is unitarely equivalent to one of the following standard type.

Let

$$K=_X^{}K_x𝑑\mu (x)$$

be a direct integral of real Hilbert spaces satisfying

$$K_{x+\delta }=K_x,K_{1x}=K_x$$

for all $`\delta \mathrm{\Delta }`$ and almost all $`xX`$. With $`H=K`$ and $`H_x=K_x`$,

$$H=_X^{}H_x𝑑\mu (x).$$

Clearly, $`H_{x+\delta }=H_x=H_{1x}`$, $`K_x`$ is a canonical real form of $`H_x`$ and $`K`$ one of $`H`$. Denote by $`\overline{}`$ the corresponding conjugations. By definition, for $`fH`$,

$$\overline{f}(x)=\overline{f(x)}.$$

This determines corresponding conjugations on the endomorphisms $`A`$ of these spaces by $`\overline{A}(f)=\overline{A(\overline{f})}`$.

###### Theorem 3.9

If $`(\mu ,\nu ,\{c_k\})`$ is a GW module modeled on the Hilbert space $`H`$ with

$$\stackrel{~}{\mu }\mu ,\nu (1x)=\nu (x),\overline{c_k(1x)}=(1)^kc_k(x),$$

then

$$H^{}=\{fH:\overline{f(x)}=\sqrt{\frac{d\mu (1x)}{d\mu (x)}}f(1x)\}$$

is an invariant real form of $`H`$. Conversely, any pair consisting of a GW module together with an invariant real form, is unitarely equivalent to one of that type.

###### Demonstration Proof

For the first assertion we just need to apply Theorem (3.5) with $`r(x)f(x)=\overline{f(x)}`$.

For the converse, start with any split module and let $`S,T,r(x),`$ be as in the proof of (3.5). In it we have fixed identifications $`\psi _x:H_xH_{1x}`$ in order to define the operator $`T`$. Explicitely, letting $`\mathrm{\Phi }(x)=\sqrt{\frac{d\stackrel{~}{\mu }(x)}{d\mu (x)}}`$, the “actual” operator is $`(\tau f)(x)=\mathrm{\Phi }(x)f(1x)`$ and

$$(Tf)(x)=\psi _x^1(\tau f)(x)=\mathrm{\Phi }(x)\psi _x^1(f(1x)).$$

If $`\stackrel{~}{\psi }_x:H_xH_{1x}`$ is another identification, the corresponding operator will be

$$(\stackrel{~}{T}f)(x)=\stackrel{~}{\psi }_x^1((\tau f)(x))=\stackrel{~}{\psi }_x^1\psi _x\psi _x^1((\tau f)(x))=h_x((Tf)(x))$$

with $`h_x=\stackrel{~}{\psi }_x^1\psi _x`$ unitary on $`H_x`$.

Define $`u(x)=H_xH_x`$ by

$$u(x)f(x)=r(x)\overline{f(x)}.$$

These are $``$-linear and norm-preserving, hence unitary and measurable in $`x`$, because $`r(x)`$ is so. Change the chosen identification $`H_xH_{1x}`$ by $`u(x)`$, so that the new operator $`T`$ will be

$$\stackrel{~}{T}f(x)=u(x)^1(Tf)(x).$$

For this identification and the equivalent real structure

$$\stackrel{~}{S}=u^1Su,$$

the function $`\stackrel{~}{r}(x)`$ is

$$\stackrel{~}{r}(x)f(x)=\stackrel{~}{S}\stackrel{~}{T}f(x)=u^1Suu(x)^1(Tf)(x)=u(x)^1STf(x)=u(x)^1r(x)f(x)=\overline{f(x)}.$$

This effectively shows that, up to equivalence, we may take $`r(x)`$ to be conjugation with respect to any basic flat field of real forms.

Since the operators $`c_k(x)`$ do not depend on the identification $`H_x=H_{1x}`$, the relations (3.6) must still hold for the new $`\stackrel{~}{r}(x)`$, which translates into $`\overline{c_k(1x)}=(1)^kc_k(x)`$.

As an application, let us describe the simplest irreducible representation of $`C_{}(Z)`$ that splits over $``$., i.e., as a representation of $`C(Z)`$. The two irreducible summands will be equivalent and truly real, in the sense that they do not arise from any complex representation of $`C_{}(Z)`$ by restriction of the scalars.

Let $`\mu =\mu _X`$ be the Haar measure on $`X`$ and $`\nu =1`$, so that $`H_x=`$, $`K_x=`$,

$$H=L_2(X)$$

(dropping the reference to the Haar measure) and the conjugation $`\overline{}`$ is given by $`\overline{f}(x)=\overline{f(x)}`$. As $`c_k`$’s, which are now functions from $`X`$ to the circle $`𝕋`$, choose

$$\begin{array}{cc}\hfill c_2\mathrm{}(x)& =1\hfill \\ \hfill c_{4\mathrm{}+1}(x)& =(1)^{x_{4\mathrm{}+3}}\hfill \\ \hfill c_{4\mathrm{}+3}(x)& =(1)^{x_{4\mathrm{}+1}}\hfill \end{array}.$$

###### Theorem 3.11

These functions satisfy (2.3) and, therefore, (2.5) defines a representation of $`C_{}(Z)`$ in $`L_2(X)`$. This representation is irreducible. The real subspace

$$L_2(X)^{}=\{fL_2(X):f(1x)=\overline{f(x)}\}$$

is invariant and irreducible under $`C(Z)`$. Furthermore, the representation so obtained does not arise from any representation of $`C_{}(Z)`$ by restriction of the scalars.

###### Demonstration Proof

The irreducibility of the corresponding GW module $`H`$ follows from the ergodicity of the Haar measure, as in (3.8).

It is straightforward to check that the functions $`c_k`$ satisfy (2.3) and (3.10), so, by Theorem (3.9), the corresponding $`𝕁`$ must leave the real form $`H^{}`$ invariant. Of course, this can be deduced by direct calculation as well, using (2.5). $`H^{}`$ must be irreducible under $`C(Z)`$, since any closed invariant subspace generates a closed $`C_{}(Z)`$-invariant subspace in $`H`$.

Finally, suppose that the representation of $`C(Z)`$ in $`H^{}`$ could be extended to one of $`C_{}(Z)`$ (in $`H^{}`$ itself). Denote by $`T`$ the operation representing multiplication by $`\sqrt{1}`$: $`T`$ is an orthogonal complex structure in $`H^{}`$ commuting with $`C(Z)`$. Its unique $``$-linear extension to all of $`H=H^{}iH^{}`$ is unitary and commutes with all the $`𝕁`$. As we have already mentioned, this implies that $`T`$ is given pointwise, by an operator-valued measurable function $`k(x)`$: $`(Tf)(x)=k(x)f(x).`$ In the present case, $`k(x)`$ is complex valued. Since $`k(x)^2=1`$, we can write it as

$$k(x)=ϵ(x)i$$

for some measurable $`ϵ:X\{\pm 1\}`$. The condition for $`T`$ to leave invariant the real form $`H^{}`$ and to commute with the representation $`𝕁`$ amount to, respectively,

$$ϵ(1x)=ϵ(x)ϵ(x+\delta _k)=ϵ(x)$$

for almost all $`x`$ and all $`k`$. The second equation implies that $`ϵ`$ is actually constant on each $`\mathrm{\Delta }`$-equivalence class. \[According to \[Go\] ???\], $`ϵ`$ must then be constant almost everywhere, contradicting the first equation. Hence, no such $`T`$ can exist. ∎

Representations with these parameters can be realized on the standard $`L_2(𝕋)`$ of complex-valued functions on the circle since, as a measure space, $`(X,\mu _X)`$ is the same as the interval $`(0,1)`$ -hence to the circle, equipped with the Lebesgue measure and $`dimH_x=1`$. In this identification, translations in $`X`$ do not correspond to rigid rotations of $`𝕋`$. However, the operation $`x1x`$ in $`X`$ (changing all the elements of $`x`$) does correspond to $`x1x`$ on $`(0,1)`$ which, on $`𝕋`$, becomes ordinary complex conjugation. The operators $`c_k`$ can then be viewed as functions

$$\stackrel{~}{c}_k:𝕋𝕋,$$

satifying, of course, (2.3). According to Theorem 3.9, those that split over $``$ can be realized with

$$L_2(𝕋)^{}=\{fL_2(𝕋):\overline{f(t)}=f(\overline{t})\}.$$

as the invariant real form. The condition on the functions $`c_k`$ for this real form to be invariant under the $`𝕁`$’s becomes

$$\overline{c_k(t)}=(1)^kc_k(\overline{t}).$$
$`(3.10)`$
for $`t𝕋`$.


text:
# Orbital order induced metal-insulator transition in La1-xCaxMnO3

## Abstract

We present evidence that the insulator to metal transition in La1-xCaxMnO3 near $`x0.2`$ is driven by the suppression of coherent Jahn-Teller distortions, originating from $`d`$ type orbital ordering. The orbital ordered state is characterised by large long-range $`Q2`$ distortions below $`T_{O^{}\text{-}O}`$. Above $`T_{O^{}\text{-}O}`$ we find evidence for coexistence between an orbital-ordered and -disordered state. This behaviour is discussed in terms of electronic phases of an orbital ordered insulating and orbital-disordered metallic states.

LaMnO3 in the ground state is an antiferromagnetic insulator with a checkerboard pattern of $`e_g`$ orbitals Jonker and van Santen (1950); Huang et al. (1998); Goodenough (1955); Elemans et al. (1971); Kugel’ and Khomskii (1973); Cussen et al. (2001). The basic exchange interactions in the manganite perovskites allow three phases: a ferromagnetic metal, a charge/orbital ordered antiferromagnetic insulator and a paramagnetic polaronic liquid. Although superexchange allows ferromagnetic interactions, the observed orbital ordering in LaMnO3 renders an overall antiferromagnetic state. When 20% to 50% holes are introduced, a ferromagnetic metallic ground state with degenerate $`e_g`$ orbitals is obtained. However, La1-xCaxMnO3, with $`0.10<x<0.20`$, has a ferromagnetic insulating ground state. This unexpected coexistence of ferromagnetic and insulating behaviour seems to contradict the conventional double and superexchange models. The LaMnO3-CaMnO3 phase diagram by Cheong and co-workers Uehara et al. (2000), sketched partially in Fig. 1, shows the doping induced ferromagnetic insulator (FI) to ferromagnetic metal (FM) transition at a critical concentration of $`x_c0.21`$. While this transition is intriguing by itself, the situation becomes more complex by the orbital order (O’) to ”not orbital ordered” (O\*) transition, deduced from anomalies in the resistivity. The origin of the coexistence of ferromagnetism with insulating behaviour is not clear, but might stem from a delicate balance of charge localisation by orbital ordering (OO), due to the Jahn-Teller (JT) effect, and ferromagnetic interactions between Mn3+-Mn4+. Neither the exact concentration dependence of this transition nor the interaction of this orbital order transition with the magnetic ordering and the temperature- or doping-induced metal-insulator transition is known. The O’-O\* transition is typically associated with a step in the resistance or a re-entrant insulating behaviour.

The phase diagram of Sr doped manganites has been explored in great detail Urushibara et al. (1995). Here the situation is more complicated than for Ca doping, because the number of phases is larger due to the rhombohedral structure at $`x>0.18`$ and the pronounced charge ordering (CO) at $`x\frac{1}{8}`$ Yamada et al. (1996). Several authors reported a JT related structural phase transition above the magnetic ordering temperature, $`T>T_c`$ at $`x0.12`$. Below $`T_c`$, a transition to CO or OO is observed, where the co-operative JT distortion is significantly reduced Argyriou et al. (1996); Endoh et al. (1999). As the transition temperatures are extremely concentration dependent, a comparison between the various reports is not straightforward. It is claimed that the intermediate phase is both ferromagnetic and metallic and exhibits static co-operative JT distortions Kawano et al. (1996); Endoh et al. (1999). Some reports clearly distinguish these two properties and combine short range order of JT distortions with metallic behaviour Dabrowski et al. (1999a). However, a general relation between the JT ordered phase and the nature of the conductivity has not been established. Also, a coincidence of the CO transition and the re-entrant insulator-metal transition is claimed. The common metal-insulator transition is indisputably associated with the ferromagnetic ordering at $`T_c`$ Urushibara et al. (1995); Endoh et al. (1999); Kawano et al. (1996); Dabrowski et al. (1999a).

The Ca doped phase diagram is somewhat less complex, as there is no orthorhombic-rhombohedral structural transition. Furthermore, the phase transitions take place at higher concentrations. As a result we can probe the ferromagnetic insulating phase at concentrations far away from $`x=\frac{1}{8}`$ to evade charge ordering. In this Letter, we explore the region where the OO phase line crosses the magnetic ordering phase line. We will show that the transition to the ferromagnetic metallic phase is controlled by the suppression of JT ordering. Our measurements show that the $`Q2`$ distortion is constant below $`T_{O^{}\text{-}O}`$. However it decreases smoothly above $`T_{O^{}\text{-}O}`$, both in the paramagnetic and in the ferromagnetic phase. We will show that the decrease is associated with phase separation in an O’ phase and an orbital disordered (O\*) phase.

The experiments were carried out on single crystals of La1-xCaxMnO3, $`x=0.16`$, $`x=0.19`$ and $`x=0.25`$, obtained by the floating zone method. The sample with $`x=0.19`$ originated from the MISIS institute, Moscow, the other two samples are grown at JRCAT, Japan. Although all crystals were twinned Van Aken et al. (2001), small mosaicity and sharp diffraction spots were observed. Resistance curves for the samples were measured using a four-point set-up. Sharp metal-insulator transitions, indicative of the good quality of the crystals are observed for La0.81Ca0.19MnO3 and La0.75Ca0.25MnO3 as shown in Fig. 2. A thin piece was cut from the crystals to be used for single crystal diffractometry. Initial measurements were carried out on an Enraf-Nonius CAD4 single crystal 4-circle diffractometer to determine the twin relations and the twin fraction volume Van Aken et al. (2001). Temperature dependent measurements between 90 K and 300 K were performed on a Bruker APEX diffractometer with an adjustable temperature set-up.

The temperature dependence of the resistivity is shown for the three samples in Fig. 2. All three samples show a local maximum at $`T_c`$. For La0.84Ca0.16MnO3 and La0.81Ca0.19MnO3, we observe at significantly lower temperatures, $`T145`$ K and $`T160`$ K respectively, that the resistivity shows a subtle and wide transition to activated behaviour. For La0.84Ca0.16MnO3 a step in the resistance is observed at $`T275`$ K.

The temperature dependence of the crystal structure of La1-xCaxMnO3, $`x=0.16`$, $`x=0.19`$ and $`x=0.25`$, has been determined by single crystal diffraction. In analogy to conventional ferromagnetic metallic La1-xCaxMnO3 systems, with $`x0.3`$ Booth et al. (1998), we expect to observe a narrowing of the distribution of Mn$``$O bond lengths below $`T_c`$ as a result of the itinerancy in the ferromagnetic, metallic regime. As soon as the JT orbital ordering sets in there will be an abrupt disproportionation of the Mn$``$O bond lengths, as observed for La1-xSrxMnO3 with $`0.11<x<0.165`$ Dabrowski et al. (1999a). The changes in the structure due to orbital ordering are described using the $`Q2`$ distortion Cussen et al. (2001).

The lattice parameters are not a very accurate probe to measure the bond disproportionation, because they are the sum of long and short bonds. However, we have shown elsewhere Van Aken et al. (2001) that the O2 positionQ (2) in $`Pnma`$ space group symmetry accurately reflects both the JT distortion and the rotation of the octahedra. Because the $`Q2`$ distortion Q (2) and the GdFeO3 rotation Glazer (1972) involve orthogonal displacements of O2, they can be accurately obtained from the fractional atomic co-ordinates of O2, as shown in Fig. 3. The final refinement, including the twin relations, yielded $`RF=0.068`$ and $`wR2=0.26`$, and is published in detail elsewhere Van Aken (2001).

Fig. 4 shows the parameter for the co-operative $`Q2`$ distortion against temperature as determined by single crystal XRD. Below $`T_{O^{}\text{-}O}`$, $`Q2`$ is constant for the samples with $`x=0.16`$ and $`x=0.19`$. For the $`x=0.25`$ sample $`Q2`$ is constant at all temperatures. Because the O2 position is not constrained in $`Pnma`$, we consider $`Q20.002`$ signalling the absence of long range JT distortions. This value is also observed for non-Jahn-Teller active systems such as AFeO3, *e.g.* $`Q2=0.0036`$ for LuFeO3 Marezio et al. (1970). We also observe in Fig. 4 that above $`T_{O^{}\text{-}O}`$ $`Q2`$ gradually decreases for $`x=0.16`$ and $`x=0.19`$. Extrapolating the data yields that near $`T300`$ K all evidence for long range JT distortions is absent.

Comparing the temperature dependence of the resistance with that of $`Q2`$, we note that the kink in $`Q2`$ is accompanied with the upturn and step in the resistance, commonly associated with $`T_{O^{}\text{-}O}`$. This is direct evidence that the ”plateau” state in $`Q2`$ is the signature for the O’ phase. These coherent distortions, associated with $`e_g`$ orbital ordering, are therefore sufficient to localise the charge carriers. Thus, orbital ordering and metallicity are mutual exclusive in the La1-xCaxMnO3 system. This confronts the model proposed by Killian and Khaliullin Kilian and Khaliullin (1999).

This model calculates the effect of orbital ordering on the kinetic energy of the valence electrons in terms of coherent and incoherent charge transport. An incoherent process consists of an electron that is excited to an orbital that violates the long range order. If the energy to occupy a symmetry breaking orbital is too high, the incoherent process is considered absent. The absence of incoherent processes will result in a large reduction of the holon band width, which can cause the metal-insulator transition. They argue that the reduction of the holon band width is too small to have a significant effect on the kinetic energy of the charge carriers. Thus, in their model, the orbital disorder-order crossover cannot be responsible for the metal-insulator transition.

However, this model neglects the influence of coherent JT lattice distortions. An incoherent process not only involves the orbital excitation energy associated with the energy difference of the two $`e_g`$ orbitals, but also compromises the $`Pnma`$ symmetry that incorporates the coherent $`Q2`$ distortions. Therefore, incoherent processes do not only involve crystal field energies, but require adjustment of the local oxygen co-ordination such that the orbitals and lattice distortions are aligned. Our main finding is that orbital ordering has a large effect on electronic conduction and moreover that metallicity only results in La1-xCaxMnO3 if the orbital degeneracy is maintained.

When holes are introduced on JT distorted Mn3+ sites, the resulting Mn4+ ions still experience a JT distorted oxygen co-ordination. The reason is that the perovskite lattice consists of corner sharing oxygen octahedra. Therefore, the oxygen position is determined by two Mn ions. Thus a Mn4+ ion co-ordinated by Mn3+ containing octahedra will still have a distortion, albeit with a smaller amplitude. This is in contrast to single ions models Kilian and Khaliullin (1999), that neglect the co-operative effect of the ordered $`Q2`$ distortions.

Nevertheless, introduction of holes in orbital ordered LaMnO3 will decrease the magnitude of the $`Q2`$ distortion. Our experimental values at 100 K are shown in Fig. 5. Clearly $`Q2`$ decreases gradually with Ca doping and no JT distortion can be observed for $`x>0.21`$. The $`Q2`$ parameter for the undoped $`e_g`$ system LaMnO3 is about four times larger than in undoped $`t_{2g}`$ systems such as YVO3 Blake et al. (2001) and YTiO3 MacLean et al. (1979). Furthermore, $`T_{O^{}\text{-}O}`$ is reduced with increased doping level. The reduction in $`Q2`$ and $`T_{O^{}\text{-}O}`$ with increased doping level is consistent with resistivity and Seebeck measurements, which showed that the activation energies for charge transport decreased with doping Palstra et al. (1997). We speculate that the disappearance of long-range orbital order is partially induced by frustrating the $`d`$ type orbital ordering by introducing holes with doping. Undoped LaMnO3 has antiferromagnetic interactions along the $`b`$ axis, which is consistent with mirror symmetry perpendicular to the $`b`$ axis and the ferrodistortive orientation of the orbitals along the $`b`$ axis. Introduction of holes will result in ferromagnetic interactions along $`b`$, resulting eventually for $`x>0.10`$ in a ferromagnetic ground state. However, a larger carrier concentration is required to suppress the orbital order and obtain degeneracy of the $`e_g`$ orbitals and thus a metallic state.

Whereas conventionally La1-xCaxMnO3 is considered to be a doped antiferromagnet in which double exchange plays a dominant role, we emphasise the dominating role of introducing holes in the orbital ordered state.

We note that the temperature dependence of the $`Q2`$ distortion is remarkably different from that observed in $`t_{2g}`$ based JT ordered systems. For these materials the JT distortion exhibits a BCS-like type temperature dependence, with the vanishing of the coherent distortion above $`T_{O^{}\text{-}O}`$. Here, we observe a rapid decrease of the coherent distortion above $`T_{O^{}\text{-}O}`$ Blake et al. (2001). We interpret this temperature dependence originating from a coexistence of an orbital ordered and orbital disordered state. We note that the measurements of integrated intensities cannot give more detail of the nature of these states. This coexistence was also observed in neutron powder diffraction experiments on La0.86Ca0.16MnO3 at room temperature Dabrowski et al. (1999b). Such structural phase separation is evidence for electronic phase separation as we associate the orbital ordered state with localised charge carriers and the orbital degenerate state with, if $`T<T_c`$, the metallic state.

In the phase diagram of La1-xSrxMnO3, the CO phase borders the FMM phase, as observed by superlattice reflections in single crystal neutron experiments Yamada et al. (1996). In contrast, for La1-xCaxMnO3 the CO phase is suppressed by the orbital ordered FMI phase. We have not observed any superlattice reflections. A possible charge ordering phase either exists at lower temperatures, $`T<90`$ K, or at a hole concentration closer to $`x=1/8`$. We note that the concept of orbital polarons might lead to low temperature charge and orbital ordering Kilian and Khaliullin (1999); Mizokawa et al. (2001). However this feature is incompatible with $`Pnma`$ symmetry, and thus can be ruled out.

We have demonstrated that the ferromagnetic metallic phase is obtained by the suppression of the long range Jahn-Teller ordering. This contrasts the common opinion that metallicity occurs if the charge carrier density exceeds a critical concentration. The O’ phase mixes with the O\* phase above $`T_{O^{}\text{-}O}`$. Above a second phase line, the transition to the O\* phase is complete. The metallic state of La1-xCaxMnO3 is bounded by ferromagnetic ordering and the absence of orbital ordering.

Stimulating discussions with Daniel Khomskii, Lou-Fé Feiner, George Sawatzky, Graeme Blake, Martine Hennion, Paolo Radaelli, Neil Mathur and Takashi Mizokawa are gratefully acknowledged. This work is supported by the Netherlands Foundation for the Fundamental Research on Matter (FOM) and by the New Energy and Industrial Technology Development Organization (NEDO) of Japan.