TRANSMISSION COEFFICIENTS FOR EVAPORATION AND CONDENSATION
TRANSMISSION COEFFICIENTS FOR EVAPORATION AND CONDENSATION
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蒸发和冷凝的传输系数
DOI：
10.1021/j100836a004
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发表时间：
1960
期刊：
影响因子：
--
通讯作者：
H. Eyring
中科院分区：
文献类型：
--
作者：
E. Mortensen;H. Eyring
绝对反应速率理论通常从平衡计算跨越势垒的速率开始，然后用传输系数对其进行修正。在某些单分子反应中，这个传输系数小于1。在这种反应中，通常没有足够的时间使内部自由度在从初始状态到激活状态的过程中达到平衡。为了修正蒸发和冷凝过程中的这种非平衡条件，将传递系数设为假定平衡时初始状态的内部配分函数与激活状态的内部配分函数之比。
The theory of absolute reaction rates usually begins with the equilibrium calculation of the rate of surmounting a barrier and then corrects thisby the transmission coefficient. In certain unimolecular reactions this transmission coefficient is less than unity. In such reactions there is often not sufficienttime for the internal degrees of freedom to equilibrate in going from the initial to activated states. To correct for this non-equilibrium condition in evaporation and condensation the transmis-sion coefficient is set equal to the ratio of the internal partition function in the initial state to the internal partition function in the activated state assuming equilibrium.