Potential energy curves using unrestricted Mo/ller–Plesset perturbation theory with spin annihilation

Abstract

Unrestricted Hartree–Fock and unrestricted Mo/ller–Plesset perturbation theory are convenient methods to compute potential energy curves for bond dissociation, since these methods approach the correct dissociation limit. Unfortunately, a spin unrestricted wave function can contain large contributions from unwanted spin states that can distort the potential energy surface significantly. The spin contamination can be removed by projection or annihilation operators. As is well known, the spin project unrestricted Hartree–Fock bond dissociation curves have a large kink at the onset of the UHF/RHF instability, and a spurious minimum just beyond. However, the spurious minimum disappears and the kink is very much less pronounced at the unrestricted Mo/ller–Plesset level with spin projection. Bond dissociation potentials for LiH and CH₄ were computed at the fourth order Mo/ller–Plesset level plus spin projection,⁴ and good agreement was found with full CI and MR‐CISD calculations.