This paper is the first of two in which the coupled cluster method (CCM) or exp(S) formalism is applied to two-component Fermi systems, the aim being to describe real metals and superconductivity. In this paper the authors concentrate on exact results and restrict ourselves to a ring approximation, applicable essentially to a high-density regime. They show that in the ground-state formalism the random phase approximation (RPA) can be formulated as a system of coupled, bilinear integral equations satisfied by functions associated with the so-called four-point functions of the system which provide a measure of the two-particle two-hole components in the true ground-state wavefunction. These equations are analysed in the dimensionless parameter formed by the ratio of the species masses and exact analytic solutions obtained. For Coulombic potentials (V 11 V 22 =V 2 12 ) they show that the exact analytic solution is unique and obtain an expression for the correlation energy. For non-Coulombic potentials (V 11 V 22 not=V 2 12 ) they indicate how to obtain a possible analytic solution. An RPA-like treatment of the one- and two-body equations in the excited-state formalism is provided for completeness.
In this second work in a series of papers the coupled-cluster or
exp(S) formalism is applied to the problem of ground-state correlations in the one-component Fermi plasma. The main approximation employed is the so-called SUB2 approximation for the two-body subsystem correlation operator
S2 which provides a measure of the two-particle---two-hole component in the true ground-state wave function, and in which the coupling to larger subsystems is neglected. The SUB2 equations for Fermi systems are brought into tractable form by a "state-averaging" procedure which we develop by analogy with the comparable Bose equations, and which is shown by comparison with earlier exact results to be accurate in the metallic density regime at about the 1% level. Our final results for metallic densities include the completely integrated and self-consistent effects of the terms which by themselves generate (i) the random-phase approximation (RPA) and its associated exact long-range screening effects, (ii) the extra random-phase approximation exchange terms necessary to keep the RPA explicitly antisymmetric, (iii) the self-consistent particle-particle ladders (LAD) that describe two-particle scattering within the many-body medium and which describe the exact short-range behavior, (iv) a class of particle-hole ladder terms, and (v) the self-consistent hole-potential terms. Particular attention is paid to the important effects caused by the interference at intermediate separations of the long-range RPA and the short-range LAD effects. By comparison with recent and essentially exact stochastic simulations of the many-body Schr\"odinger equation, our results are seen to be accurate to about 1% for metallic densities, and hence to provide what is probably the currently best microscopic description available for this system. We show also that even in the low-density limit the SUB2 approximation provides a good "translationally-invariant-solid" description of both charged Fermi and Bose systems in this exact Wigner crystal regime.
The ground-state correlation energy calculated in the random-phase approximation (RPA) is known to be identical to that calculated using a subset of terms appearing in coupled-cluster theory with double excitations (CCD). In particular, for particle-hole (ph) RPA this equivalence requires keeping only those terms that generate time-independent ring diagrams, and for particle-particle (pp) RPA it requires keeping only those terms that generate ladder diagrams. Here I show that these identities extend to excitation energies, for which those calculated in each RPA are identical to those calculated using approximations to equation-of-motion coupled-cluster theory with double excitations (EOM-CCD). The equivalence requires three approximations to EOM-CCD: first, the ground-state CCD amplitudes are obtained from the ring-CCD or ladder-CCD equations (the same as for the correlation energy); second, the EOM eigenvalue problem is truncated to the minimal subspace, which is one particle + one hole for ph-RPA and two particles or two holes for pp-RPA; third, the similarity transformation of the Fock operator must be neglected, as it corresponds to a Brueckner-like dressing of the single-particle propagator, which is not present in the conventional RPA.
We propose a novel approach to electron correlation for multireference systems. It is based on particle-hole (ph) and particle-particle (pp) theories in the second-order, developed in the random phase approximation (RPA) framework for multireference wave functions. We show a formal correspondence (duality), between contributions to the correlation energy in the ph and pp pictures. It allows us to describe correlation energy by rigorously combining pp and ph terms, avoiding correlation double counting. The multireference ph, pp, and the combined correlation methods are applied to ground and excited states of systems in the intermediate and strong correlation regimes and compared with the multireference second-order perturbation method (MRPT2). It is shown that the pp approximation fails to describe dissociation of multiple bonds. The ph-pp combined method is overall superior to both ph and pp alone. It parallels good accuracy of the second-order perturbation theory for ground states and singlet excitation energies. For the singlet-triplet gaps of biradicals its accuracy is significantly better. This is impressive, taking into account that it relies only on one- and two-body density matrices, while MRPT2 methods typically require density matrices up to the four-body.
A methodology is introduced for the systematic treatment of electron-electron correlations in solids and other interacting quantum
N-particle systems. The method is developed within the framework of electronic structure theory (band theory) but, in contrast to conventional approaches, which are based on the single-particle picture, it is formulated within a many-particle picture in which
n particles in
d-dimensional phase space are treated as a single particle in a phase space of
nd dimensions. In this phase space, interparticle interactions appear as external potentials allowing the treatment of the system of particles through the use of single-particle methods, while at the same time allowing a systematic, direct, and nonperturbative treatment of interparticle interactions. The method makes use of the invariance of the Hamiltonian describing an interacting-particle system under partitioning into subsystems of
n particles. This treatment leads to exact results in the limit $n\ensuremath{\rightarrow}N$. Based on such partitioning, we propose a generalization of density functional theory and an appropriately defined local density approximation to treat the interactions between the
n-particle units in a system of
N> n particles. This approach yields
n-particle correlated densities and
n-particle states which can be used in an analysis of the electronic properties of materials, such as total energy, phase stability, electronic transport, and others. We use the formal construct of multiple-scattering theory to develop the method for the calculation of the two-particle electronic structure of a solid and the corresponding total energy of the ground state. We also illustrate some of the properties of the method in terms of a Hubbard model Hamiltonian on a linear ring. Various features of the method and further possible applications are presented in a discussion section.
A general theory of long range correlations in the ground state of a closed shell nucleus is outlined, using a number of ideas introduced or adumbrated, but not always successfully developed, in previous work of the authors and others. These include the following: (i) Any operator can be formally expressed as a series in particle-hole (p-h) excitation and destruction operators which should converge rapidly for a suitable choice of single-particle basis at the closed shells. By means of these relations and with the help of sum rules all observables can be computed without the explicit use of wave functions. (ii) For a fixed choice of single-particle basis, the ground state energy can be computed from a variational principle in which in lowest nontrivial approximation, in consequence of (i), the parameters are amplitudes of the same type as occur in the random phase approximation (RPA). The precise relation to RPA is fully detailed. (iii) The single particle basis chosen is the natural orbital basis of Lowdin, which presents itself as the obvious choice both for formulation of the dynamics and for the algorithm of solution. (iv) Though the theory deals with pairs of fermion operators, particular attention is paid that all Pauli principle restrictions are satisfied. (v) It is verified that in the perturbation limit, known results are reproduced. The method is generally applicable to any system for which the correlations can be viewed as particle-hole excitations with respect to a reference Slater determinant.