Nikitin E E, Troe J
Max-Planck-Institut für biophysikalische Chemie, Am Fassberg 11, D-37077, Goettingen, Germany.
Phys Chem Chem Phys. 2006 May 7;8(17):2012-6. doi: 10.1039/b517843f. Epub 2006 Apr 13.
The general quasi-classical treatment for collision-induced vibrational transitions in diatomic molecules, under near-adiabatic conditions, is used to derive quantum corrections for probabilities, calculated in the external field approximation originally used by Landau and Teller. The quantum corrections are expressed through the Landau-Teller classical collision time. The first-order correction to the classical exponent restores detailed balance for up- and down-transitions and does not depend on the properties of the bath except for its temperature. The limits of applicability of the first-order correction are discussed.
在近绝热条件下，采用双原子分子中碰撞诱导振动跃迁的一般准经典处理方法，推导了概率的量子修正，这些概率是在朗道和泰勒最初使用的外场近似中计算得到的。量子修正通过朗道 - 泰勒经典碰撞时间来表示。对经典指数的一阶修正恢复了向上和向下跃迁的细致平衡，并且除了温度外不依赖于浴的性质。讨论了一阶修正的适用范围。
