Lam Yan-Choi, Soudackov Alexander V, Hammes-Schiffer Sharon
Department of Chemistry , Yale University , 225 Prospect Street , New Haven , Connecticut 06520 , United States.
J Phys Chem Lett. 2019 Sep 19;10(18):5312-5317. doi: 10.1021/acs.jpclett.9b01984. Epub 2019 Aug 28.
Proton discharge on metal electrodes, also denoted the Volmer reaction, is a critical step in a wide range of electrochemical processes. This electrochemical proton-coupled electron transfer (PCET) reaction is predominantly electronically adiabatic in aqueous solution and is typically treated as fully adiabatic. Recently, a theoretical model for this PCET reaction was developed to generate the vibronic free energy surfaces as functions of a collective solvent coordinate and the distance of the proton-donating acid from the electrode. Herein a unified formulation is devised to describe such PCET reactions in terms of a curve crossing between two diabatic vibronic states corresponding to the lowest two proton vibrational states, employing an interpolation scheme that spans the adiabatic transition state theory, nonadiabatic Fermi golden rule, and solvent-controlled regimes. In contrast to previous treatments, application of this formulation to the aqueous Volmer reaction highlights the importance of vibrational nonadiabaticity and solvent dynamics. The calculated transfer coefficients and kinetic isotope effects are in reasonable agreement with experimental measurements. These fundamental insights have broad implications for understanding electrochemical processes.
质子在金属电极上的放电,也被称为Volmer反应,是众多电化学过程中的关键步骤。这种电化学质子耦合电子转移(PCET)反应在水溶液中主要是电子绝热的,通常被视为完全绝热。最近,针对这种PCET反应开发了一种理论模型,以生成作为集体溶剂坐标和质子供体酸与电极之间距离函数的振动电子自由能面。在此,设计了一种统一的公式,根据对应于最低两个质子振动态的两个非绝热振动状态之间的曲线交叉来描述此类PCET反应,采用了跨越绝热过渡态理论、非绝热费米黄金规则和溶剂控制区域的插值方案。与先前的处理方法不同,将此公式应用于水溶液中的Volmer反应突出了振动非绝热性和溶剂动力学的重要性。计算得到的传递系数和动力学同位素效应与实验测量结果合理吻合。这些基本见解对理解电化学过程具有广泛的意义。