Curve crossing formulation for proton transfer reactions in solution
Curve crossing formulation for proton transfer reactions in solution
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DOI：
10.1021/jp9522324
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发表时间：
1996-01-25
影响因子：
--
通讯作者：
Hynes, JT
中科院分区：
文献类型：
--
作者：
Borgis, D;Hynes, JT
建立了质子耦合范围内质子转移速率常数的朗道-齐纳曲线交叉公式。这种方法跨越了弱耦合状态，其中转移是一个非绝热的质子隧道，到强耦合状态，在反应过渡态，质子运动是一个量子化的振动，位于质子坐标的势垒之上。该理论要求质子转移溶质与周围极性溶剂存在强耦合，并考虑质子转移的重粒子振动运动的影响，给出了质子耦合强度和重粒子运动振动频率在不同极限下的速率常数的解析公式。
A Landau-Zener curve crossing formulation is developed for proton transfer rate constants over the range of proton coupling. This approach spans the weak coupling regime, where the transfer is a nonadiabatic proton tunneling, to the strong coupling regime, where at the reaction transition state the proton motion is a quantized vibration lying above the barrier in the proton coordinate. The theory requires that there is strong coupling of the proton transfer solute to the surrounding polar solvent and includes the influence of the vibrational motion of the heavy particles between which the proton transfers, Analytic formulas are given for the rate constants in various limits of the proton coupling strength and the vibrational frequency of the heavy particle motion.