论文标题
一般的非绝热量子插入近似
A general non-adiabatic quantum instanton approximation
论文作者
论文摘要
我们提出了一种通用的量子激体方法，用于计算具有两个电子状态的系统和电子耦合的任意值的系统的反应速率。我们称这种新方法称为非绝热量子Instanton（NAQI）近似，以黄金规则限制减少了Wolynes理论，并在绝热限制中降低了最近提出的预测的量子Instanton（PQI）方法。与这两个早期理论一样，NAQI方法基于对反应性通量自相关函数的时间积分的鞍点近似，尽管对产品状态的投影算子的一般定义具有广义定义。我们通过与一维散射问题的精确速率进行比较来说明该方法的准确性，并讨论其对更复杂反应的适用性。
We present a general quantum instanton approach to calculating reaction rates for systems with two electronic states and arbitrary values of the electronic coupling. This new approach, which we call the non-adiabatic quantum instanton (NAQI) approximation, reduces to Wolynes theory in the golden rule limit and to a recently proposed projected quantum instanton (PQI) method in the adiabatic limit. As in both of these earlier theories, the NAQI approach is based on making a saddle point approximation to the time integral of a reactive flux autocorrelation function, although with a generalised definition of the projection operator onto the product states. We illustrate the accuracy of the approach by comparison with exact rates for one dimensional scattering problems and discuss its applicability to more complex reactions.
