FIRST PRINCIPLES MOLECULAR DYNAMICS INVOLVING EXCITED STATES AND NONADIABATIC TRANSITIONS

Abstract

Extensions of traditional molecular dynamics to excited electronic states and non-Born–Oppenheimer dynamics are reviewed focusing on applicability to chemical reactions of large molecules, possibly in condensed phases. The latter imposes restrictions on both the level of accuracy of the underlying electronic structure theory and the treatment of nonadiabaticity. This review, therefore, exclusively deals with ab initio "on the fly" molecular dynamics methods. For the same reason, mainly mixed quantum-classical approaches to nonadiabatic dynamics are considered.