文献类型：期刊文献

英文题名：Solvent Effect on Cation?3π Interactions: A First-Principles Study

作者：Mu, Liuhua[1,2,3];Jiang, Jie[1];Li, Xiao-Yan[4];Sheng, Shiqi[5]

机构：[1]Ningbo Univ, Sch Phys Sci & Technol, Ningbo 315211, Peoples R China;[2]Univ Chinese Acad Sci, Wenzhou Inst, Wenzhou 325001, Peoples R China;[3]Univ Chinese Acad Sci, Sch Phys Sci, Beijing 100049, Peoples R China;[4]Northwestern Univ, Dept Chem, Evanston, IL 60208 USA;[5]East China Univ Sci & Technol, Sch Phys, Shanghai 200237, Peoples R China

年份：2024

卷号：29

期号：21

外文期刊名：MOLECULES

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001351829100001)】；

基金：This research was funded by the National Natural Science Foundation of China (12005062 and 12405036) and the Postdoctoral Fellowship Program of CPSF under grant number GZC20232610.

语种：英文

外文关键词：cation circle times 3 pi interaction; solvent effect; aromatic box; first-principles calculation

摘要：Cation circle times 3 pi interactions play a special role in the behaviors of biological molecules and carbon-based materials in aqueous solutions, yet the effects of solvation on these interactions remain poorly understood. This study examines the sequential attachment of water molecules to cation circle times 3 pi systems (cation = Li+, Na+, K+), revealing that solvation influences interaction strengths in opposing ways: solvation of the metal cation decreases the strengths of cation circle times 3 pi interactions, while the solvation of the benzene molecule increases the strengths of cation circle times 3 pi interactions, compared with the strengths of cation circle times 3 pi interactions in the gas phase. The mechanism analyses revealed that in the presence of surrounding water molecules, the stability of cation circle times 3 pi systems is generally enhanced by cation-pi, pi-pi, water-pi, and water-ion interactions, while water-water interactions typically have a destabilizing effect. In addition, the primary effect of water molecules at different adsorption sites is to modulate the Coulombic multipole-multipole interactions and the overlap between monomeric charge distributions, thereby influencing the changes in strengths of cation circle times 3 pi interactions. Moreover, AIMD simulations further underscore the practical significance of cation circle times 3 pi interactions. These findings provide valuable insights into the structures and the strengths of cation circle times 3 pi interactions with the effect of solvation.