A comparison of hydride, hydrogen atom, and proton-coupled electron transfer reactions is presented. Herein, hydride and hydrogen atom transfer refer to reactions in which the electrons and protons transfer between the same donor and acceptor, while proton-coupled electron transfer (PCET) refers to reactions in which the electrons and protons transfer between different centers. Within these definitions, hydride and hydrogen atom transfer reactions are typically electronically adiabatic, hence evolving on a single electronic surface. In contrast, PCET reactions are often electronically nonadiabatic since the electron transfers a longer distance through a proton transfer interface. For all three types of reactions, solute reorganization is important, particularly the hydrogen donor--acceptor mode. Solvent reorganization is critical for hydride transfer and PCET, which involve significant solute charge redistribution, but not for hydrogen atom transfer. Theoretical descriptions and simulation methodology for all three types of reactions are presented, as well as experimentally relevant applications to hydride transfer in enzymes and PCET in solution.

中文翻译：

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氢化物，氢原子和质子耦合电子转移反应的比较。

氢化物，氢原子和质子耦合的电子转移反应进行了比较。在此，氢化物和氢原子转移是指电子和质子在同一给体和受体之间转移的反应，而质子偶合电子转移（PCET）是指电子和质子在不同中心之间转移的反应。在这些定义内，氢化物和氢原子转移反应通常是电子绝热的，因此在单个电子表面上发展。相反，由于电子通过质子传递界面传递更长的距离，因此PCET反应通常在电子上是非绝热的。对于所有这三种类型的反应，溶质重组都很重要，尤其是氢供体-受体模式。溶剂重组对于氢化物转移和PCET至关重要，后者涉及大量的溶质电荷再分配，但对于氢原子转移却不重要。本文介绍了这三种反应的理论描述和模拟方法，以及在酶和溶液中PCET的氢化物转移方面的实验相关应用。