A general non-adiabatic quantum instanton approximation.
A general non-adiabatic quantum instanton approximation.
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一般的非绝热量子瞬时近似。
DOI：
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发表时间：
2020
影响因子：
4.4
通讯作者：
D. Manolopoulos
中科院分区：
文献类型：
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作者：
Joseph E Lawrence;D. Manolopoulos
我们提出了一个通用的量子瞬子方法来计算具有两个电子态和任意值的电子耦合的体系的反应速率。这种新的方法，我们称之为非绝热量子瞬子(NAQI)近似，简化为黄金法则极限下的Wolynes理论和最近提出的绝热极限下的投影量子瞬子方法。在这两个早期的理论中，Naqi方法是基于对反应通量自相关函数的时间积分进行鞍点近似的基础上的，尽管具有对乘积状态的投影算符的广义定义。我们通过与一维散射问题的精确速率的比较来说明该方法的精度，并讨论了它对更复杂的反应的适用性。
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 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 generalized 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.
DOI：
10.1021/acs.jpca.9b00877
发表时间：
2019-02
期刊：
The journal of physical chemistry. A
影响因子：
--
作者：
Xuecheng Tao;Philip Shushkov;Thomas F. Miller
通讯作者：
Xuecheng Tao;Philip Shushkov;Thomas F. Miller
DOI：
10.1063/1.5005544
发表时间：
2017-09
期刊：
The Journal of chemical physics
影响因子：
--
作者：
Xuecheng Tao;Philip Shushkov;Thomas F. Miller
通讯作者：
Xuecheng Tao;Philip Shushkov;Thomas F. Miller