Nonadiabatic Field: A Conceptually Novel Approach for Nonadiabatic Quantum Molecular Dynamics.

Abstract

Reliable trajectory-based nonadiabatic quantum dynamics methods at the atomic/molecular level are critical for the practical understanding and rational design of many important processes in real large/complex systems, where the quantum dynamical behavior of electrons and that of nuclei are coupled. The paper reports latest progress of nonadiabatic field (NaF), a conceptually novel approach for nonadiabatic quantum dynamics with independent trajectories. Substantially different from the mainstreams of Ehrenfest-like dynamics and surface hopping methods, the nuclear force in NaF involves the nonadiabatic force arising from the nonadiabatic coupling between different electronic states, in addition to the adiabatic force contributed by a single adiabatic electronic state. NaF is capable of faithfully describing the interplay between electronic and nuclear motion in a broad regime, which covers where the relevant electronic states keep coupled in a wide range or all the time and where the bifurcation characteristic of nuclear motion is essential. NaF is derived from the exact generalized phase space formulation with coordinate-momentum variables, where constraint phase space (CPS) is employed for discrete electronic-state degrees of freedom (DOFs) and infinite Wigner phase space is used for continuous nuclear DOFs. We propose efficient integrators for the equations of motion of NaF in both adiabatic and diabatic representations. Since the formalism in the CPS formulation is not unique, NaF can in principle be implemented with various phase space representations of the time correlation function (TCF) for the time-dependent property. They are applied to a suite of representative gas-phase and condensed-phase benchmark models where numerically exact results are available for comparison. It is shown that NaF is relatively insensitive to the phase space representation of the electronic TCF and will be a potential tool for practical and reliable simulations of the quantum mechanical behavior of both electronic and nuclear dynamics of nonadiabatic transition processes in real systems.