金属／水界面的第一性原理分子动力学计算与应用

电化学界面在能量的存储和转化方面起到了关键的作用，然而目前我们对于它的认知还十分有限，这主要是因为电化学界面非常复杂，利用实验手段观测极具挑战性。理论计算可以为实验观测方法提供重要支持和有效补充，然而方法的缺失使得电化学界面的模拟一直是计算电化学领域的一个重要难题。近期申请人发展了基于第一性原理分子动力学界面模拟和电极电势计算的新方法，并首次得出金属／水界面参比到标准氢电极的零电荷电位，可以直接与实验值精确对比。在本申请项目中，我们将进一步发展该方法计算模拟界面双电层，研究表面带电情况下的金属／水界面（以Pt(111)/水界面作为主体研究对象），旨在深入理解不同电位下的电化学界面成分、结构、相互作用、电场分布、双电层电容等性质，建立一个新的界面双电层理论模型。更进一步，我们将基于新发展的双电层理论模型，探讨界面电场、结构等因素对于电催化反应的影响，旨在突破广泛应用的Norskov模型方法。

Electrochemical interface plays a key role in energy storage and conversion, however its microscopic properties are not well known yet. It is because electrochemical interface is complicated and very challenging to use experimental techniques to directly monitor. Theoretical simulation can complement the experiments for investigating the electrochemical interfaces, while due to the lack of methods, how to simulate electrochemical interface is always a problem in the field of computational electrochemistry. Recently, we have methods developed for first principle based molecular dynamics calculations of interfaces and electrode potential, and for the first time apply for studying metal/water interfaces at potential of zero charge, the obtained values are in good agreement with experimental data. In this project, we will further develop our methods for studying the charged metal/water interfaces (take Pt(111)/water interface as the example), aiming to deeply understand the composition, structure, mutual interaction, electric field distribution and double layer capacitance of the interfaces at various electrode potentials, and propose a new theoretical model of the interfacial electric double layer. Furthermore, based on our simulated Pt(111)/water interfaces, we will investigate the effect of interfacial electric field and structure on electrochemical reactions, aiming to go beyond Norskov method for electrocatalytic reaction study.