First-principles predictions play an important role in understanding chemistry at the electrochemical interface. Electronic structure calculations are straightforward for vacuum interfaces, but do not easily account for the interfacial fields and solvation that fundamentally change the nature of electrochemical reactions. Prevalent techniques for first-principles prediction of electrochemical processes range from expensive explicit solvation using ab initio molecular dynamics, through a hierarchy of continuum solvation techniques, to neglecting solvation and interfacial field effects entirely. Currently, no single approach reliably captures all relevant effects of the electrochemical double layer in first-principles calculations.

This review systematically lays out the relation between all major approaches to first-principles electrochemistry, including the key approximations and their consequences for accuracy and computational cost. Focusing on ab initio methods for thermodynamic properties of aqueous interfaces, we first outline general considerations for modeling electrochemical interfaces, including solvent and electrolyte dynamics and electrification. We then present the specifics of various explicit and implicit models of the solvent and electrolyte. Finally, we discuss the compromise between computational efficiency and accuracy, and identify key outstanding challenges and future opportunities in the wide range of techniques for first-principles electrochemistry.

第一性原理预测在理解电化学界面化学方面发挥着重要作用。电子结构计算对于真空界面来说很简单，但不容易考虑从根本上改变电化学反应性质的界面场和溶剂化。电化学过程第一原理预测的常用技术包括从头开始分子动力学的昂贵的显式溶剂化，通过连续溶剂化技术的层次结构，到完全忽略溶剂化和界面场效应。目前，没有一种方法可以可靠地捕获电化学双层在第一原理计算中的所有相关效应。

这篇综述系统地阐述了第一原理电化学的所有主要方法之间的关系，包括关键的近似值及其对准确性和计算成本的影响。重点关注水界面热力学性质的从头计算方法，我们首先概述了电化学界面建模的一般考虑因素，包括溶剂和电解质动力学和电气化。然后，我们介绍了溶剂和电解质的各种显式和隐式模型的细节。最后，我们讨论了计算效率和准确性之间的折衷，并确定了第一原理电化学广泛技术中的关键突出挑战和未来机遇。