A Practical Diabatisation Scheme for Use with the Direct-Dynamics Variational Multi-Configuration Gaussian Method.
A Practical Diabatisation Scheme for Use with the Direct-Dynamics Variational Multi-Configuration Gaussian Method.
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DOI：
10.1021/acs.jpca.5b07921
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发表时间：
2015-10
期刊：
影响因子：
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通讯作者：
Gareth W Richings;G. Worth
中科院分区：
文献类型：
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作者：
Gareth W Richings;G. Worth
提出了一种计算量子核动力学的直接动力学变分多组态高斯方法中多电子态的动态非绝热处理方法。该方法基于绝热-非绝热变换矩阵沿构成核波函数的高斯基函数所遵循的路径的传播，通过使用将该矩阵与电子态之间的非绝热矢量耦合项联系起来的众所周知的微分方程。文中描述了该方法的实现，并以丁三烯阳离子的基态和第一激发态为例进行了测试计算，从而可以与早期的正则化非简并方案以及在预先计算的势能面上的全部核动力学进行比较。这一新方案被称为传播衰减法。
A method for diabatising multiple electronic states on-the-fly within the direct dynamics variational multi-configuration Gaussian method for calculating quantum nuclear dynamics is presented. The method is based upon the propagation of the adiabatic-diabatic transformation matrix along the paths followed by the Gaussian basis functions that constitute the nuclear wave function, by use of a well-known differential equation relating the matrix and the nonadiabatic vector coupling terms between the electronic states. The implementation of the method is described, and test calculations are presented using the ground and first-excited states of the butatriene cation as an example, allowing comparison to the earlier regularisation diabatisation scheme as well as to full nuclear dynamics on a precomputed potential energy surface. The new scheme is termed propagation diabatisation.