Simplification of solvation shell with water clusters in the simulation of electrochemical nitrogen reduction reaction

• Published in: The Journal of chemical physics 2024-11, Vol.161 (18)
• Main Authors: Liu, Han-Xuan, Huang, Zheng-Qing, Gao, Xin, Yang, Guidong, Chang, Chun-Ran
• Format: Article
• Language: English
• Subjects: Chemical reduction; Clusters; Nitrogen; Solvation; Solvents
• ISSN: 0021-9606; 1089-7690; 1089-7690
• DOI: 10.1063/5.0230137

Electrochemical methods for nitrogen reduction have received extensive attention due to the mild reaction conditions. In order to gain an insight into the mechanism of the electrochemical nitrogen reduction process, theoretical simulations are necessary. However, current simulation studies contain many imprecise approximations that may hinder the real recognition of the reaction process. Although solvation methods have recently been developed to provide efficient descriptions, their further applications are hindered by controversy over modeling of solvents and the enormous computational effort required. In this work, we simplify the solvation conditions by using water clusters and compare them with an accurate water layer model. The results demonstrate that the simplified water clusters can effectively capture protons, simulate the surface electric environment, and enable the calculation of the activation energy of the reaction. This method offers an affordable approach for simulating the surface potentials and solvents and provides a new reference for the theoretical study of the electrochemical nitrogen reduction reaction.