Gu Bing
Department of Chemistry and Department of Physics, Westlake University, Hangzhou, Zhejiang 310030, China.
Institute of Natural Sciences, Westlake Institute for Advanced Study, Hangzhou, Zhejiang 310024, China.
J Chem Theory Comput. 2024 Apr 9;20(7):2711-2718. doi: 10.1021/acs.jctc.3c01317. Epub 2024 Mar 27.
We develop and implement an exact conical intersection nonadiabatic wave packet dynamics method that combines the local diabatic representation, Strang splitting for the total molecular propagator, and discrete variable representation with uniform grids. By employing the local diabatic representation, this method captures all nonadiabatic effects, including nonadiabatic transitions, electronic coherences, and geometric phase. Moreover, it is free of singularities in the first and second derivative couplings and does not require the electronic wave function to be continuous with respect to the nuclear coordinates. We further show that in contrast to the adiabatic representation, the split-operator method can be directly applied to the full molecular propagator with the locally diabatic ansatz. The Fourier series, employed as the primitive nuclear basis functions, is universal and can be applied to all types of reactive coordinates. The combination of local diabatic representation, Strang splitting, and Fourier basis allows numerically exact modeling of conical intersection quantum dynamics directly with adiabatic electronic states that can be obtained from standard electronic structure computations.
我们开发并实现了一种精确的锥形交叉非绝热波包动力学方法，该方法结合了局域 diabatic 表象、用于总分子传播子的 Strang 分裂以及具有均匀网格的离散变量表象。通过采用局域 diabatic 表象，该方法能够捕捉所有非绝热效应，包括非绝热跃迁、电子相干性和几何相位。此外，它在一阶和二阶导数耦合中没有奇点，并且不要求电子波函数相对于核坐标连续。我们进一步表明，与绝热表象不同，分裂算符方法可以直接应用于具有局域 diabatic 假设的全分子传播子。作为原始核基函数使用的傅里叶级数具有通用性，可应用于所有类型的反应坐标。局域 diabatic 表象、Strang 分裂和傅里叶基的结合使得能够直接用可从标准电子结构计算获得的绝热电子态对锥形交叉量子动力学进行数值精确建模。
