Nonadiabatic Molecular Dynamics by Multiconfiguration Pair-Density Functional Theory
Nonadiabatic Molecular Dynamics by Multiconfiguration Pair-Density Functional Theory
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DOI：
10.1021/acs.jctc.1c01048
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发表时间：
2022-01-14
影响因子：
5.5
通讯作者：
Gagliardi, Laura
中科院分区：
文献类型：
--
作者：
Calio, Paul B.;Truhlar, Donald G.;Gagliardi, Laura
本文首次实现了多组态对密度泛函理论（MC-PDFT）从头算分子动力学。MC-PDFT是一种多参考电子结构方法，在许多情况下具有与完整的有源空间二阶微扰理论（CASPT 2）相似的精度（甚至更高的精度），计算成本显著降低。在这项研究中，我们引入MC-PDFT分析梯度SHARC分子动力学程序从头算，非绝热分子动力学模拟。我们验证我们的实施通过检查系统间的交叉动力学的硫代甲醛，我们观察到极好的协议与最近的CASPT 2和实验结果。此外，与MC-PDFT，我们可以进行动力学模拟与12电子在10轨道活动空间，这是计算太昂贵的直接动力学与CASPT 2。
We present the first implementation of multiconfiguration pair-density functional theory (MC-PDFT) ab initio molecular dynamics. MC-PDFT is a multireference electronic structure method that in many cases has a similar accuracy (or even better accuracy) the complete active space second-order perturbation theory (CASPT2) at a significantly lower computational cost. In this study, we introduced MC-PDFT analytical gradients into the SHARC molecular dynamics program for ab initio, nonadiabatic molecular dynamics simulations. We verify our implementation by examining the intersystem crossing dynamics of thioformaldehyde, and we observe excellent agreement with recent CASPT2 and experimental findings. Moreover, with MC-PDFT, we could perform dynamics simulations with the 12 electron in 10 orbitals active space that was computationally too expensive for direct dynamics with CASPT2.