Miller William H, Cotton Stephen J
Department of Chemistry and Kenneth S. Pitzer Center for Theoretical Chemistry, University of California and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
J Chem Phys. 2015 Apr 7;142(13):131103. doi: 10.1063/1.4916945.
It is noted that the recently developed symmetrical quasi-classical (SQC) treatment of the Meyer-Miller (MM) model for the simulation of electronically non-adiabatic dynamics provides a good description of detailed balance, even though the dynamics which results from the classical MM Hamiltonian is "Ehrenfest dynamics" (i.e., the force on the nuclei is an instantaneous coherent average over all electronic states). This is seen to be a consequence of the SQC windowing methodology for "processing" the results of the trajectory calculation. For a particularly simple model discussed here, this is shown to be true regardless of the choice of windowing function employed in the SQC model, and for a more realistic full classical molecular dynamics simulation, it is seen to be maintained correctly for very long time.
值得注意的是,最近开发的用于模拟电子非绝热动力学的迈耶 - 米勒(MM)模型的对称准经典(SQC)处理方法,即使由经典MM哈密顿量产生的动力学是“埃伦费斯特动力学”(即,原子核上的力是所有电子态的瞬时相干平均值),也能很好地描述细致平衡。这被认为是SQC窗口化方法“处理”轨迹计算结果的结果。对于这里讨论的一个特别简单的模型,无论SQC模型中使用的窗口化函数如何选择,都证明是正确的,并且对于更现实的全经典分子动力学模拟,在很长时间内都能正确保持。