基于能量的轨线面跳跃新退相干修正方法

New Energy-Based Decoherence Correction Approaches for Trajectory Surface Hopping

本文受轨线分叉修正面跳跃(BCSH)方法[J.Xu and L.Wang,J.Chem.Phys.150,164101(2019)]的启发,提出了两种轨线面跳跃新退相干时间计算公式.本研究的线型和指数型公式均将退相干时间刻画为绝热势能面之间能差的函数,能够准确地描述BCSH预测的由波包反射导致的退相干效应.在包含了200个多样化的系列模型中,采用不同的初始核动量,以精确全量子解为参考,对涉及的参数进行了系统训练.相比广泛使用的退相干公式,两种新方法在Tully的三个标准模型中都显著地提高了可靠性,并保持高计算效率.

Inspired by the branching corrected surface hopping(BCSH)method[J.Xu and L.Wang,J.Chem.Phys.150,164101(2019)],we present two new decoherence time formulas for trajectory surface hopping.Both the proposed linear and exponential formulas characterize the decoherence time as functions of the energy difference between adiabatic states and correctly capture the decoherence effect due to wave packet reflection as predicted by BCSH.The relevant parameters are trained in a series of 200 diverse models with different initial nuclear momenta,and the exact quantum solutions are utilized as references.As demonstrated in the three standard Tully models,the two new approaches exhibit significantly higher reliability than the widely used counterpart algorithm while holding the appealing efficiency,thus promising for nonadiabatic dynamics simulations of general systems.