Accurate quantum dynamics of electronically nonadiabatic chemical reactions in the DH2+ system
Accurate quantum dynamics of electronically nonadiabatic chemical reactions in the DH2+ system
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DOI：
10.1063/1.1418252
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发表时间：
2002-01
影响因子：
4.4
通讯作者：
Hideyuki Kamisaka;W. Bian;K. Nobusada;Hiroki Nakamura
中科院分区：
文献类型：
--
作者：
Hideyuki Kamisaka;W. Bian;K. Nobusada;Hiroki Nakamura
采用超球坐标方法，利用量子化学从头计算方法构造的新势能面，对J=0（J，总角动量量子数）的DH ~（2+）体系进行了三维精确量子动力学计算.不仅电子非绝热反应，即，研究了反应性电荷转移过程，也研究了电子绝热反应和电子非绝热非反应过程。由于电子绝热地面上的深阱，出现了大量的共振，电子绝热反应大多是统计的。沿着势交叉缝的非绝热跃迁导致偏离统计行为，并发现了一些有趣的动力学特征。
Three-dimensional accurate quantum dynamics calculations are carried out for the DH2+ system for J=0 (J, total angular momentum quantum number) by the hyperspherical coordinate approach with use of the new potential energy surfaces constructed based on the recent ab initio quantum chemical calculations. Not only electronically nonadiabatic reactions, i.e., reactive charge transfer processes, but also electronically adiabatic reactions and electronically nonadiabatic nonreactive processes are investigated. Because of the deep well on the electronically adiabatic ground surface, there appear a large number of resonances and the electronically adiabatic reactions are mostly statistical. Nonadiabatic transitions along the potential crossing seam cause deviations from the statistical behavior and some interesting dynamical features are found.