Evaluation of canonical and microcanonical nonadiabatic reaction rate constants by using the Zhu-Nakamura formulas.
Evaluation of canonical and microcanonical nonadiabatic reaction rate constants by using the Zhu-Nakamura formulas.
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DOI：
10.1063/1.1801971
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发表时间：
2004-10
期刊：
影响因子：
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通讯作者：
Yi Zhao;G. Mil'nikov;Hiroki Nakamura
中科院分区：
文献类型：
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作者：
Yi Zhao;G. Mil'nikov;Hiroki Nakamura
本文考虑了非绝热化学反应的热速率常数和微正则速率常数的计算问题。我们不使用传统的过渡态理论，而是使用一个广义的缝面，并在Zhu-Nakamura理论的基础上引入了一个与坐标相关的有效非绝热跃迁几率的概念，它可以很好地处理非绝热隧穿。该方法可与Monte Carlo方法相结合，适用于复杂体系的化学反应。该方法在较宽的能量和温度范围内工作良好。数值试验还表明，采用广义缝面并考虑非绝热隧穿效应对准确计算热速率常数是十分必要的。
We consider a problem of calculating both thermal and microcanonical rate constants for nonadiabatic chemical reactions. Instead of using the conventional transition state theory, we use a generalized seam surface and introduce a concept of a coordinate dependent effective nonadiabatic transition probability based on the Zhu-Nakamura theory which can treat the nonadiabatic tunneling properly. The present approach can be combined with Monte Carlo method so as to be applicable to chemical reactions in complicated systems. The method is demonstrated to work well in wide energy and temperature range. Numerical tests also show that it is very essential for accurate evaluation of the thermal rate constant to use the generalized seam surface and take into account the nonadiabatic tunneling effect.