Mo/ller–Plesset energy derivatives

Abstract

A Mo/ller–Plesset energy functional (Lagrangian) which is variational in all variables (the Lagrange multipliers, the orbital rotation parameters, and the orbital energies) is constructed. The variational property ensures that the responses of the orbitals and orbital energies to order n in geometrical perturbations determine the energy derivatives to order 2n+1. The Lagrange multipliers satisfy the somewhat stronger 2n+2 rule. The multipliers, orbital rotations, and orbital energy responses are determined from coupled perturbed Hartree–Fock-type equations using an exponential parametrization of the orbitals. This ensures that the orbital rotations and energy responses are treated in the same way and calculated from a single set of linear equations. Explicit expressions for energy derivatives up to third order are derived for the second-order Mo/ller–Plesset energy.