Non-adiabatic transition probability dependence on conical intersection topography
Non-adiabatic transition probability dependence on conical intersection topography
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DOI：
10.1063/1.4967259
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发表时间：
2016-11-21
影响因子：
4.4
通讯作者：
Hynes, James T.
中科院分区：
文献类型：
--
作者：
Malhado, Joao Pedro;Hynes, James T.
本文基于在一般圆锥交点附近的单一直线轨迹的非绝热跃迁概率的Landau-Zener方程，导出了轨迹分布通过一般圆锥交点（CI）的非绝热跃迁概率的封闭解析表达式。我们研究了非绝热跃迁概率随地形特征的变化，并发现，对于相同的穿越速度，峰值和倾斜的CIs之间促进非绝热衰变的效率没有内在差异，结果与通常持有的观点相反。因此，任何尖顶过坡的CIs效率的提高都是由于动力效应，而不是由于地形起源转移概率的增加。研究还表明，跃迁概率一般取决于接近CI的方向，并且在质量尺度坐标中，坐标的减少质量可以通过其对CI地形的影响来影响跃迁概率。所得的预测结果与表面跳跃模拟结果比较好。AIP出版社出版。
We derive a closed form analytical expression for the non-adiabatic transition probability for a distribution of trajectories passing through a generic conical intersection (CI), based on the Landau-Zener equation for the non-adiabatic transition probability for a single straight-line trajectory in the CI's vicinity. We investigate the non-adiabatic transition probability's variation with topographical features and find, for the same crossing velocity, no intrinsic difference in efficiency at promoting non-adiabatic decay between peaked and sloped CIs, a result in contrast to the commonly held view. Any increased efficiency of peaked over sloped CIs is thus due to dynamical effects rather than to any increased transition probability of topographical origin. It is also shown that the transition probability depends in general on the direction of approach to the CI, and that the coordinates' reduced mass can affect the transition probability via its influence on the CI topography in mass-scaled coordinates. The resulting predictions compare well with surface hopping simulation results. Published by AIP Publishing.