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

机译:均值场混合半经典方法的评估:平衡种群和算法稳定性

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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.
机译:我们研究了几种最新的均值半经典动力学方法,重点是针对长时间(平衡)群体恢复详细平衡的能力。我们特别关注Miller和Cotton的[J.物理化学[117,7190(2013)]建议在Ehrenfest动力学上同时包括零点电子能量和窗口。我们研究了三种状态:电子耦合弱的谐波表面,电子耦合强的谐波表面和电子耦合弱的非谐波表面。在大多数情况下,最近对Ehrenfest动力学的补充是对均值场理论的有力改进。但是,对于包含零点电子能量的方法,我们表明,非谐势能表面经常导致数值不稳定性,这是由负人口和力引起的。我们还表明,尽管负力的作用可能隐藏在谐波系统中,但最终的平衡极限仍取决于任何加窗和零点能量参数。由AIP Publishing发布。

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