化学
离解(化学)
光解
激发态
动力学同位素效应
势能
阿伦尼乌斯图
光化学
动能
活化能
阿累尼乌斯方程
量子产额
量子隧道
原子物理学
物理化学
物理
量子力学
荧光
氘
作者
Hanjie Ying,Hongbo Zhao,Wenji Wang
摘要
Abstract The photodissociation of phenol is a prototype of the photoinduced hydrogen detachment reaction. The dissociation rates of phenol through the excited S 1 state are calculated with the quantum instanton method in full dimensionality. The Arrhenius plot of the rates shows that the quantum tunneling dominates the OH bond dissociation at low temperatures. The degrees of freedom of phenyl ring (C 6 H 5 ) play extremely important roles in the dissociation of phenol. Fixing the phenyl ring at the equilibrium geometry can only provide reliable rates between 400 K and 800 K. The motions of phenyl ring have an impact on enhancing the dissociation by lowering the free energy barrier. The larger the amplitudes of the phenyl ring motions are, the more the free energy barrier will be reduced. The dissociation rates of C 6 H 5 OH are much larger than those of C 6 H 5 OD, which is due to the zero‐point energy and entropy effects.
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