Self-consistent field perturbation theory of molecular vibrations

Abstract

Perturbation theory is used to perform non-iterative calculations of energy eigenvalues of the coupled ordinary differential equations that result from imposing separability assumptions in terms of normal coordinates on vibrational wavefunctions. Various model Hamiltonians with 2 or 3 coupled normal modes are studied and the increase of computational cost with the number of degrees of freedom is analysed. Quadratic Padé approximants of the perturbation expansions are rapidly convergent, and directly yield complex numbers for resonance eigenvalues. For a 3-mode system, results are obtained within partial separability assumptions, with a pair of modes left coupled. Large-order perturbation theory with partial separability is suggested as an alternative to low-order exact perturbation theory.