Diagonalizing the Born-Oppenheimer Hamiltonian via Moyal Perturbation Theory, Nonadiabatic Corrections and Translational Degrees of Freedom

Abstract

This article describes a method for calculating higher order or nonadiabatic corrections in Born-Oppenheimer theory and its interaction with the translational degrees of freedom. The method uses the Wigner-Weyl correspondence to map nuclear operators into functions on the classical phase space and the Moyal star product to represent operator multiplication on those functions. The result is a power series in $κ^2$, where $κ=(m/M)^{1/4}$ is the usual Born-Oppenheimer parameter. The lowest order term is the usual Born-Oppenheimer approximation while higher order terms are nonadiabatic corrections. These are needed in calculations of electronic currents, momenta and densities. The method was applied to Born-Oppenheimer theory by Littlejohn and Weigert (1993), in a treatment that notably produced the correction $K_{22}$ to the Born-Oppenheimer Hamiltonian (see {\em infra}). Recently Matyus and Teufel (2019) have applied an improved and more elegant version of the method to Born-Oppenheimer theory, and have calculated the Born-Oppenheimer Hamiltonian for multiple potential energy surfaces to order $κ^6$. One of the shortcomings of earlier methods is that the separation of nuclear and electronic degrees of freedom takes place in the context of the exact symmetries (for an isolated molecule) of translations and rotations, and these need to be a part of the discussion. This article presents an independent derivation of the Moyal expansion in molecular Born-Oppenheimer theory, with special attention to the translational degrees of freedom. We show how electronic currents and momenta can be calculated within the framework of Moyal perturbation theory; we derive the transformation laws of the electronic Hamiltonian, the electronic eigenstates, and the derivative couplings under translations.