文献类型：期刊文献

英文题名：A reaction density functional theory study of solvent effect in the nucleophilic addition reactions in aqueous solution

作者：Cai, Cheng[1,2,3];Tang, Weiqiang[1,2];Qiao, Chongzhi[1,2];Bao, Bo[1,2];Xie, Peng[4];Zhao, Shuangliang[1,2,4];Liu, Honglai[3]

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]East China Univ Sci & Technol, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[4]Guangxi Univ, Sch Chem & Chem Engn, Guangxi Key Lab Petrochem Resource Proc & Proc In, Nanning 530004, Peoples R China

年份：2022

卷号：7

期号：4

起止页码：782

外文期刊名：GREEN ENERGY & ENVIRONMENT

收录：;EI(收录号：20211410182067);WOS:【SCI-EXPANDED(收录号:WOS:000803021400009)】；

基金：This work is supported by National Natural Science Foundation of China (Nos. 91934302, 21878078 and 21808056).

语种：英文

外文关键词：Reaction density functional theory; Nucleophilic addition; Solvent effect; Charge models

摘要：Whereas the proper choice of reaction solvent constitutes the cornerstone of the green solvent concept, solvent effects on chemical reactions are not mechanistically well understood due to the lack of feasible molecular models. Herein, by taking the case study of nucleophilic addition reaction in aqueous solution, we extend the proposed multiscale reaction density functional theory (RxDFT) method to investigate the intrinsic free energy profile and total free energy profile, and study the solvent effect on the activation and reaction free energy for the nucleophilic addition reactions of hydroxide anion with methanal and carbon dioxide in aqueous solution. The predictions of the free energy profile in aqueous solution for these two nucleophilic addition reactions from RxDFT have a satisfactory agreement with the results from the RISM and MD-FEP simulation. Meanwhile, the solvent effect is successfully addressed by examining the difference of the free energy profile between the gas phase and aqueous phase. In addition, we investigate the solvent effect on the reactions occurred near solid-liquid interfaces. It is shown that the activation free energy is significantly depressed when reaction takes place in the region within 10 angstrom distance to the substrate surface owing to the decrease of hydration free energy at the solid-liquid interface. (C) 2020 Institute of Process Engineering, Chinese Academy of Sciences. Publishing services by Elsevier B.V.on behalf of KeAi Communications Co., Ltd.