Ab initio surface hopping excited-state molecular dynamics approach on the basis of spin-orbit coupled states: An application to the A-band photodissociation of CH3I
Ab initio surface hopping excited-state molecular dynamics approach on the basis of spin-orbit coupled states: An application to the A-band photodissociation of CH3I
复制标题
基于自旋轨道耦合态的从头算表面跳跃激发态分子动力学方法：CH3I A 波段光解离的应用
DOI：
10.1002/jcc.25727
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
M. Kamiya and T. Taketsugu
中科院分区：
文献类型：
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作者：
伊豫谷 登士翁;吉原 直樹;飯笹 佐代子(編著）;M. Kamiya and T. Taketsugu
从头算分子动力学方法已扩展到多态动力学，其基础是通过对角元素中的多态二阶多参考微扰理论能量和非对角元素中的状态平均完整活性空间自洽场水平的自旋轨道耦合项对自旋轨道耦合矩阵进行对角化获得的自旋轨道耦合电子态。利用自旋轨道耦合波函数的数值微分计算的非绝热耦合项和解析的非绝热耦合项，采用表面跳跃方案，显式地考虑了自旋轨道耦合态的非绝热跃迁.本方法被应用于碘甲烷的A带光解，CH 3 I +hv→ CH 3 + I（2 P3/2）/I*（2 P1/2），Amatsu，Yabushita和Morokuma报道了开创性的理论工作。所得结果较好地再现了实验的分支比和离解产物的能量分布。© 2018 Wiley Periodicals，Inc.
Ab initio molecular dynamics approach has been extended to multi‐state dynamics on the basis of the spin–orbit coupled electronic states that are obtained through diagonalization of the spin–orbit coupling matrix with the multi‐state second‐order multireference perturbation theory energies in diagonal elements and the spin–orbit coupling terms at the state‐averaged complete active space self‐consistent field level in off‐diagonal elements. Nonadiabatic transitions over the spin–orbit coupled states were taken into account explicitly by a surface hopping scheme with utilizing the nonadiabatic coupling terms calculated by numerical differentiation of the spin–orbit coupled wavefunctions and analytical nonadiabatic coupling terms. The present method was applied to the A‐band photodissociation of methyl iodide, CH3I +hv→ CH3+ I (2P3/2)/I* (2P1/2), for which a pioneering theoretical work was reported by Amatatsu, Yabushita, and Morokuma. The present results reproduced well the experimental branching ratio and energy distributions in the dissociative products. © 2018 Wiley Periodicals, Inc.