马库斯理论
电子转移
高斯分布
电子
溶剂化电子
化学物理
工作(物理)
化学
统计物理学
计算化学
原子物理学
物理
热力学
量子力学
物理化学
动力学
反应速率常数
放射分析
水溶液
作者
Pauf Neupane,Ankita Katiyar,David M. Bartels,Ward H. Thompson
标识
DOI:10.1021/acs.jpclett.2c02168
摘要
Reactions of the hydrated electron with a wide variety of substrates have been found to exhibit unusually similar activation energies in a manner incompatible with Marcus electron transfer theory. Given the fundamental linear response assumption of Marcus theory, one possible explanation for this apparent failure is that the underlying free energy surfaces governing the reactions are not harmonic; i.e., hydrated electron structural fluctuations exhibit non-Gaussian behavior. In this work, we test this hypothesis by using simulations to calculate the hydrated electron vertical detachment energy distribution. We consider both cavity and noncavity models for the hydrated electron, between which the actual hydrated electron behavior is expected to lie. Our results identify a possible origin for non-Gaussian behavior of the hydrated electron but show that it is not of sufficient magnitude to explain the failure of Marcus theory to describe its reactions. Thus, other explanations must be sought.
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