Nuclear-electronic orbital Ehrenfest dynamics.

Abstract

The recently developed real-time nuclear-electronic orbital (RT-NEO) approach provides an elegant framework for treating electrons and selected nuclei, typically protons, quantum mechanically in nonequilibrium dynamical processes. However, the RT-NEO approach neglects the motion of the other nuclei, preventing a complete description of the coupled nuclear-electronic dynamics and spectroscopy. In this work, the dynamical interactions between the other nuclei and the electron-proton subsystem are described with the mixed quantum-classical Ehrenfest dynamics method. The NEO-Ehrenfest approach propagates the electrons and quantum protons in a time-dependent variational framework, while the remaining nuclei move classically on the corresponding average electron-proton vibronic surface. This approach includes the non-Born-Oppenheimer effects between the electrons and the quantum protons with RT-NEO and between the classical nuclei and the electron-proton subsystem with Ehrenfest dynamics. Spectral features for vibrational modes involving both quantum and classical nuclei are resolved from the time-dependent dipole moments. This work shows that the NEO-Ehrenfest method is a powerful tool to study dynamical processes with coupled electronic and nuclear degrees of freedom.