Proton-coupled electron transfer in solution, proteins, and electrochemistry.
Proton-coupled electron transfer in solution, proteins, and electrochemistry.
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DOI：
10.1021/jp805876e
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发表时间：
2008-11-13
期刊：
影响因子：
--
通讯作者：
Soudackov AV
中科院分区：
文献类型：
--
作者：
Hammes-Schiffer S;Soudackov AV
本文综述了质子耦合电子转移（PCET）反应理论研究的最新进展。这些反应在广泛的生物过程中以及在燃料电池、太阳能电池、化学传感器和电化学装置中发挥重要作用。一个统一的理论框架已经发展到描述顺序和协调的PCET，以及氢原子转移（HAT）。一个定量诊断已被提出来区分HAT和PCET的电子nonadiabaticity的程度，其中HAT对应于电子绝热质子转移和PCET对应于电子非绝热质子转移。在这两种情况下，整个反应通常是振动非绝热的。用电子-质子振动态之间的非绝热跃迁描述PCET反应，导出了一系列不同极限下的速率常数表达式。这些表达式说明了溶剂对电子和质子转移的响应以及质子供体-受体振动运动的影响。溶剂和蛋白质的环境可以表示为一个介电连续或描述与明确的分子动力学。这些理论处理已被应用到许多PCET反应在溶液和蛋白质。还推导了电化学PCET的非均相速率常数和电流密度的表达式，并将其应用于模型系统。
Recent advances in the theoretical treatment of proton-coupled electron transfer (PCET) reactions are reviewed. These reactions play an important role in a wide range of biological processes, as well as in fuel cells, solar cells, chemical sensors, and electrochemical devices. A unified theoretical framework has been developed to describe both sequential and concerted PCET, as well as hydrogen atom transfer (HAT). A quantitative diagnostic has been proposed to differentiate between HAT and PCET in terms of the degree of electronic nonadiabaticity, where HAT corresponds to electronically adiabatic proton transfer and PCET corresponds to electronically nonadiabatic proton transfer. In both cases, the overall reaction is typically vibronically nonadiabatic. A series of rate constant expressions have been derived in various limits by describing the PCET reactions in terms of nonadiabatic transitions between electron-proton vibronic states. These expressions account for the solvent response to both electron and proton transfer and the effects of the proton donor-acceptor vibrational motion. The solvent and protein environment can be represented by a dielectric continuum or described with explicit molecular dynamics. These theoretical treatments have been applied to numerous PCET reactions in solution and proteins. Expressions for heterogeneous rate constants and current densities for electrochemical PCET have also been derived and applied to model systems.
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影响因子：
15
作者：
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