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Non-adiabatic transition probability dependence on conical intersection topography

机译:非绝热过渡概率依赖于锥形交叉地形

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摘要

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.
机译:我们基于一条直线轨迹的非绝热转变概率的Landau-Zener方程,得出通过一般圆锥形相交(CI)的轨迹分布的非绝热转变概率的闭合形式解析表达式在CI附近。我们研究了具有地形特征的非绝热转变概率的变化,发现对于相同的穿越速度,在促进峰值和倾斜CI之间非绝热衰减的效率上没有内在差异,这与通常持有的观点相反。因此,在倾斜的CI上达到峰值的任何效率提高都是由于动力效应,而不是由于地形起点的转换概率增加。还表明,过渡概率通常取决于到达CI的方向,并且坐标的减小质量可以通过其对质量缩放坐标中CI拓扑的影响来影响过渡概率。所得的预测结果与表面跳变仿真结果具有很好的比较。

著录项

  • 作者

    Malhado JP; Hynes JT;

  • 作者单位
  • 年度 2016
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  • 原文格式 PDF
  • 正文语种 ENG
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