English

The correlation energy as an explicit functional of the one-particle density matrix from a determinantal reference state

Chemical Physics 2007-05-23 v2 Atomic Physics

Abstract

Using an approach based on many body perturbation theory, the correlation energy \cEco\cEco is expressed as an explicit functional of ρ1\rho_1, vv, and vsv_s, where ρ1\rho_1 is the one-particle density matrix from the noninteracting, or reference, determinantal-state; vv is the external potential from the interacting, or target, state; vsv_s is the (kernel of the) external potential from the noninteracting determinantal-state. In other words we have \cEco[ρ1,v,vs]\cEco[\rho_1,v,v_s]. Anther possibility is the following explicit functional: \cEco[ρ1,vco,vs]\cEco[\rho_1,v_{\text{co}},v_s], where vcov_{\text{co}} is the (kernel of the) correlation potential from the noninteracting Hamiltonian. The proposed method can, in principle, be used to compute \cEco\cEco in a very accurate and efficient manner, since, like the Kohn--Sham approach, there are no virtual orbitals to consider. However, in contrast to the Kohn--Sham approach, \cEco\cEco is a known, explicit functional that can be approximated in a systematic manner. For simplicity, we only consider noninteracting closed-shell states and target states that are nondegenerate, singlet ground-states; so, in that case, ρ1\rho_1 denotes the spin-less one-particle density matrix from the determinantal reference state.

Keywords

Cite

@article{arxiv.physics/0506186,
  title  = {The correlation energy as an explicit functional of the one-particle density matrix from a determinantal reference state},
  author = {James Finley},
  journal= {arXiv preprint arXiv:physics/0506186},
  year   = {2007}
}