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Communication: Smoothing out excited-state dynamics: Analytical gradients for dynamically weighted complete active space self-consistent field

机译:通信:消除激发态动力学:动态加权的完整活动空间自洽场的分析梯度

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摘要

State averaged complete active space self-consistent field (SA-CASSCF) is a workhorse for determining the excited-state electronic structure of molecules, particularly for states with multireference character; however, the method suffers from known issues that have prevented its wider adoption. One issue is the presence of discontinuities in potential energy surfaces when a state that is not included in the state averaging crosses with one that is. In this communication I introduce a new dynamical weight with spline (DWS) scheme that mimics SA-CASSCF while removing energy discontinuities due to unweighted state crossings. In addition, analytical gradients for DWS-CASSCF (and other dynamically weighted schemes) are derived for the first time, enabling energy-conserving excited-state ab initio molecular dynamics in instances where SA-CASSCF fails. (C) 2014 AIP Publishing LLC.
机译:状态平均的完整活动空间自洽场(SA-CASSCF)是确定分子的激发态电子结构的主力军,特别是对于具有多参考特征的状态。但是,该方法存在已知问题,阻碍了其广泛采用。一个问题是,当不包括在状态平均中的一个状态与一个平均状态相交时,势能表面中存在不连续性。在本交流中,我介绍了一种新的带样条的动态权重(DWS)方案,该方案模仿了SA-CASSCF,同时消除了由于未加权状态交叉而导致的能量不连续性。此外,首次导出了DWS-CASSCF(和其他动态加权方案)的分析梯度,从而在SA-CASSCF失效的情况下实现了节能的从头开始的分子动力学。 (C)2014 AIP Publishing LLC。

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