An Improved Ehrenfest Approach to Model Correlated Electron-Nuclear Dynamics

TL;DR

This paper introduces Ehrenfest-Plus, an enhanced mixed quantum-classical method for simulating correlated electron-nuclear dynamics, improving accuracy while maintaining efficiency in modeling non-adiabatic processes.

Contribution

It develops a length gauge effective Hamiltonian and a coupled Gaussian wavepacket parameterization to better capture electron-nuclear correlations in mixed dynamics.

Findings

Ehrenfest-Plus achieves high accuracy in model tests.

The approach clarifies boundary conditions in surface hopping.

It maintains computational efficiency for complex systems.

Abstract

Mixed quantum-classical mechanics descriptions are critical to modeling coupled electron-nuclear dynamics, i.e. non-adiabatic molecular dynamics, relevant to photochemical and photophysical processes. We argue that, for polyatomic molecules, such mixed dynamics can not be efficiently described in terms of a matrix gauge potential and develop the concept of a `length gauge' effective Hamiltonian, which helps clarifying certain aspects for the popular non-adiabatic computational approaches. In particular, within such an effective Hamiltonain formalism one readily derives the momentum rescaling boundary condition, used in the surface hopping algorithms. Furthermore, using the new formalism, we introduce a coupled Gaussian wavepacket parameterization of the nuclear wavefunction, which generalizes the Ehrenfest approach to account for electron-nuclei correlations. We test this new approach, Ehrenfest-Plus, on the standard set of model problems that probe electron-nuclear correlation in non-adiabatic transitions. The high accuracy of our approach, combined with mixed-quantum classical efficiency, opens a path for improved simulation of non-adiabatic molecular dynamics in realistic molecular systems.