On the time-dependent Born–Oppenheimer approximation

Abstract In this paper, we consider the time-dependent Born–Oppenheimer approximation (BOA) of a classical quantum molecule involving a possibly large number of nuclei and electrons, described by a Schrödinger equation. In the spirit of Born and Oppenheimer’s original idea, we study quantitatively the approximation of the molecular evolution. We obtain an iterable approximation of the molecular evolution to arbitrary order, and we derive an effective equation for the reduced dynamics involving the nuclei equivalent to the original Schrödinger equation and containing no electron variables. We estimate the coefficients of the new equation and find tractable approximations for the molecular dynamics going beyond the one corresponding to the original Born and Oppenheimer approximation.