The multi-configuration electron–nuclear dynamics method

An approach to the correlated quantum dynamics of electrons and nuclei is proposed. It is an ab initio method, based on a multi-configuration expansion of the full molecular wave function. The objective of this development is to be able to describe the correlated motion of electrons in molecules beyond the fixed-nuclei approximation. Neither potential energy surfaces nor diabatic couplings need to be calculated, and Pulay forces do not appear. The method is illustrated by application to the 12 + 1 dimensional LiH molecule.