Implementation of surface hopping molecular dynamics using semiempirical methods
Implementation of surface hopping molecular dynamics using semiempirical methods
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DOI：
10.1016/j.chemphys.2008.01.044
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发表时间：
2008-06-16
期刊：
影响因子：
2.3
通讯作者：
Thiel, W.
中科院分区：
文献类型：
--
作者：
Fabiano, E.;Keal, T. W.;Thiel, W.
一个分子动力学驱动程序和表面跳跃算法的非绝热动力学已经实现的MNDO半质子电子结构软件包的发展版本。所需的能量，梯度和非绝热耦合有效地评估飞行使用半经验配置相互作用方法。讨论了核运动和量子振幅随时间演化的算法选择，并分析了计算非绝热耦合的不同方案。分子轨道跟踪和电子状态的重要性，强调在配置相互作用计算的上下文中。该方法适用于三个案例研究（乙烯，甲亚胺离子，和甲亚胺）使用正交化校正OM2哈密顿。在所有三种情况下，衰变时间和动力学路径类似的高层次从头计算结果。(c)2008 Elsevier B.V.保留所有权利。
A molecular dynamics driver and surface hopping algorithm for nonadiabatic dynamics has been implemented in a development version of the MNDO semiernpirical electronic structure package. The required energies, gradients and nonadiabatic couplings are efficiently evaluated on the fly using semiempirical configuration interaction methods. The choice of algorithms for the time evolution of the nuclear motion and quantum amplitudes is discussed, and different schemes for the computation of nonadiabatic couplings are analysed. The importance of molecular orbital tracking and electronic state following is underlined in the context of configuration interaction calculations. The method is applied to three case studies (ethylene, methaniminium ion, and methanimine) using the orthogonalization corrected OM2 Hamiltonian. In all three cases decay times and dynamics paths similar to high-level ab initio results are obtained. (c) 2008 Elsevier B.V. All rights reserved.