Tavernelli Ivano, Tapavicza Enrico, Rothlisberger Ursula
Laboratory of Computational Chemistry and Biochemistry, Ecole Polytechnique Federale de Lausanne, Lausanne CH-1015, Switzerland.
J Chem Phys. 2009 Mar 28;130(12):124107. doi: 10.1063/1.3097192.
A method is developed to compute the nonadiabatic coupling vectors (NACVs) between electronic ground and excited states as well as between any possible pair of excited states within the framework of linear response time-dependent density functional theory (TDDFT) in the adiabatic approximation. The development is an extension to our previous work on surface hopping dynamics [E. Tapavicza et al., Phys. Rev. Lett. 98, 023001 (2007)] for which we improve the description of the TDDFT approximation of the excited state wavefunctions by means of linear response orbitals. The method is first validated on the H + H(2) system that has a region of strong coupling near the conical intersection at the equilateral geometry. These results confirm the quality and the numerical efficiency of the approach, which has an accuracy comparable to the one achieved with wavefunction-based methods. Finally, we apply the method to the calculation of the NACVs of protonated formaldimine (NH(2)CH(2)(+)) along a surface hopping trajectory initiated in the second excited state.
在绝热近似下的线性响应含时密度泛函理论（TDDFT）框架内，开发了一种计算电子基态与激发态之间以及任意一对可能的激发态之间非绝热耦合矢量（NACVs）的方法。该开发是对我们先前关于表面跳跃动力学的工作[E. Tapavicza等人，《物理评论快报》98, 023001 (2007)]的扩展，为此我们通过线性响应轨道改进了对激发态波函数的TDDFT近似描述。该方法首先在H + H(2)系统上得到验证，该系统在等边几何构型的锥形交叉点附近有一个强耦合区域。这些结果证实了该方法的质量和数值效率，其精度与基于波函数的方法相当。最后，我们将该方法应用于计算质子化甲亚胺（NH(2)CH(2)(+)）在从第二激发态开始的表面跳跃轨迹上的NACVs。
