Proton-Coupled Electron Transfer: Moving Together and Charging Forward.
Proton-Coupled Electron Transfer: Moving Together and Charging Forward.
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DOI：
10.1021/jacs.5b04087
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发表时间：
2015-07-22
影响因子：
15
通讯作者：
Hammes-Schiffer S
中科院分区：
文献类型：
--
作者：
Hammes-Schiffer S
质子耦合电子转移（PCET）在化学和生物学中无处不在。本综述讨论了PCET领域的最新进展和当前面临的挑战，重点强调了理论和计算的作用。总结了基本的理论概念，并给出了速率常数和动力学同位素效应的表达式。还描述了用于计算分子电催化剂的还原电位和pKa值的计算方法，以及对线性相关性和非无辜配体的见解。此外，讨论了用于模拟光激发PCET的非绝热动力学的计算方法。介绍了PCET在溶液、蛋白质、电化学和光诱导过程中的代表性应用，突出了理论和实验研究之间的相互作用。针对每种应用类型概述了当前的挑战和建议的未来方向，最后对未来进行了总体展望。
Proton-coupled electron transfer (PCET) is ubiquitous throughout chemistry and biology. This Perspective discusses recent advances and current challenges in the field of PCET, with an emphasis on the role of theory and computation. The fundamental theoretical concepts are summarized, and expressions for rate constants and kinetic isotope effects are provided. Computational methods for calculating reduction potentials and pKa’s for molecular electrocatalysts, as well as insights into linear correlations and non-innocent ligands, are also described. In addition, computational methods for simulating the nonadiabatic dynamics of photoexcited PCET are discussed. Representative applications to PCET in solution, proteins, electrochemistry, and photoinduced processes are presented, highlighting the interplay between theoretical and experimental studies. The current challenges and suggested future directions are outlined for each type of application, concluding with an overall view to the future.