Geminal perturbation theory based on the unrestricted Hartree–Fock wavefunction

Abstract

A perturbative correction exploiting natural orbitals and the pair function structure of the unrestricted Hartree-Fock (UHF) wavefunction is devised. The method offers a simple framework for describing multireference systems where static correlation is captured by UHF. The UHF wavefunction is built of two-electron fragments (geminals), involving both singlet and triplet (ms = 0) parts. At order zero of the perturbative treatment, configuration interaction coefficients of UHF geminals are relaxed. The zero order Hamiltonian is of the Dyall-type, including explicit two-electron interaction within geminals and leading to a formal 6th power scaling. Adopting an effective one-electron zero order Hamiltonian term for the subset of virtual orbitals reduces scaling of the correction step to 4th power. Formal properties of the proposed schemes are discussed. Energetic data and natural occupation numbers of illustrative test systems are used to assess the new approach. The cases where the wavefunction becomes essentially spin pure at the level of reference show good performance. Spin contamination remaining at order zero is found to undermine the perturbative correction.