Hammes-Schiffer Sharon, Soudackov Alexander V
Department of Chemistry, 104 Chemistry Building, Pennsylvania State University, University Park, Pennsylvania 16802, USA.
J Phys Chem B. 2008 Nov 13;112(45):14108-23. doi: 10.1021/jp805876e. Epub 2008 Oct 9.
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.
本文综述了质子耦合电子转移(PCET)反应理论处理方面的最新进展。这些反应在广泛的生物过程以及燃料电池、太阳能电池、化学传感器和电化学装置中都起着重要作用。现已开发出一个统一的理论框架,用于描述相继和协同的PCET以及氢原子转移(HAT)。有人提出了一种定量诊断方法,根据电子非绝热程度来区分HAT和PCET,其中HAT对应于电子绝热质子转移,而PCET对应于电子非绝热质子转移。在这两种情况下,整体反应通常都是振转非绝热的。通过用电子 - 质子振动态之间的非绝热跃迁来描述PCET反应,在各种极限情况下推导出了一系列速率常数表达式。这些表达式考虑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。溶剂和蛋白质环境可以用介电连续介质来表示,也可以用显式分子动力学来描述。这些理论处理方法已应用于溶液和蛋白质中的众多PCET反应。还推导了电化学PCET的异质速率常数和电流密度的表达式,并将其应用于模型系统。