文献类型：期刊文献

英文题名：Dynamical density functional theory for solvation dynamics in polar solvent: Heterogeneous effect of solvent orientation

作者：Li, Yu[1,2];Qing, Leying[1,2];Yu, Hongping[1,2];Peng, Yangfeng[1,2];Xu, Xiaofei[1,2];Li, Ping[1,2];Zhao, Shuangliang[1,2,3,4]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Sch Chem Engn, Shanghai 200237, Peoples R China;[3]Guangxi Univ, Guangxi Key Lab Petrochem Resource Proc & Proc In, Nanning 530004, Peoples R China;[4]Guangxi Univ, Sch Chem & Chem Engn, Nanning 530004, Peoples R China

年份：2021

卷号：246

外文期刊名：CHEMICAL ENGINEERING SCIENCE

收录：;EI(收录号：20213210733888);WOS:【SCI-EXPANDED(收录号:WOS:000702894400016)】；

基金：This work is supported by National Natural Science Foundation of China (Nos. 91934302, 21978079, U1707602 and 21878078) and the Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology (2020Z002) .

语种：英文

外文关键词：Solvation dynamics; Polar solvent; Charge variation; Dynamical molecular density functional theory; Acetonitrile

摘要：While understanding the mechanism of the solvation dynamics in polar liquid solvents is of fundamental importance, an efficient molecular theory that can capture the microscopic solvation structure and dynamics is still under development. Herein, we extend the dynamical density functional theory to describe the solvation dynamics in polar solvents by incorporating with the molecular version of classical density functional theory. The proposed theoretical model is then applied to probe the solvation dynamics of acetonitrile solvent near individual ionic solutes. Results show the heterogeneous effect of solvent orientation surrounding charged solute plays an important role in determining the characteristic of solvation dynamics. The orientation-dependent solvation free energy at solute-unfavored orientations monotonically decays, while that at solute-favored orientations reaches a minimum value rapidly by fast adsorption of solvent molecules and then increases to a plateau owning to solvent-solvent correlation. This unravels that the solvent translation and rotation are induced firstly by the solute-solvent interaction and then driven by the solvent-solvent correlation. This work not only casts molecular insights but also provides a feasible tool to explore the solvation dynamics in polar solvents. (c) 2021 Elsevier Ltd. All rights reserved.