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.

第一性原理的预测在理解电化学界面的化学过程中起着重要作用。电子结构的计算对于真空界面很简单，但是并不能轻易说明界面场和溶剂化问题，这些界面和溶剂化从根本上改变了电化学反应的性质。用于电化学过程的第一性原理预测的普遍技术，从使用从头算分子动力学的昂贵的显式溶剂化，到连续溶剂化技术的层级，到完全忽略溶剂化和界面场效应，不一而足。当前，在第一性原理计算中，没有任何一种方法能够可靠地捕获电化学双层的所有相关影响。

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，包括关键的近似及其对准确性和计算成本的影响。着重于从头开始的水界面热力学性质的方法，我们首先概述了对电化学界面建模的一般考虑，包括溶剂和电解质动力学以及带电。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的广泛技术中的主要挑战和未来机遇。