An assessment of mean-field mixed semiclassical approaches: Equilibrium populations and algorithm stability

作者:Bellonzi Nicole*; Jain Amber; Subotnik Joseph E
来源:Journal of Chemical Physics, 2016, 144(15): 154110.
DOI:10.1063/1.4946810

摘要

We study several recent mean-field semiclassical dynamics methods, focusing on the ability to recover detailed balance for long time (equilibrium) populations. We focus especially on Miller and Cotton's [J. Phys. Chem. A 117, 7190 (2013)] suggestion to include both zero point electronic energy and windowing on top of Ehrenfest dynamics. We investigate three regimes: harmonic surfaces with weak electronic coupling, harmonic surfaces with strong electronic coupling, and anharmonic surfaces with weak electronic coupling. In most cases, recent additions to Ehrenfest dynamics are a strong improvement upon mean-field theory. However, for methods that include zero point electronic energy, we show that anharmonic potential energy surfaces often lead to numerical instabilities, as caused by negative populations and forces. We also show that, though the effect of negative forces can appear hidden in harmonic systems, the resulting equilibrium limits do remain dependent on any windowing and zero point energy parameters. Published by AIP Publishing.

  • 出版日期2016-4-21