Madelung Transform and Variational Asymptotics in Born-Oppenheimer Molecular Dynamics

Abstract

While Born-Oppenheimer molecular dynamics (BOMD) has been widely studied by resorting to powerful methods in mathematical analysis, this paper presents a geometric formulation in terms of Hamilton’s variational principle and Euler-Poincaré reduction by symmetry. Upon resorting to the Lagrangian hydrodynamic paths made available by the Madelung transform, we show how BOMD arises by applying asymptotic methods to the variational principles underlying different continuum models and their particle closure schemes. In particular, after focusing on the hydrodynamic form of the fully quantum dynamics, we show how the recently proposed bohmion scheme leads to an on-the-fly implementation of BOMD. In addition, we extend our analysis to models of mixed quantum-classical dynamics.

This work was made possible through the support of Grant 62210 from the John Templeton Foundation. The opinions expressed in this publication are those of the authors and do not necessarily reflect the views of the John Templeton Foundation.