Solvation structure and transport of acidic protons in ionic liquids:: A first-principles simulation study

被引:54
作者
Del Pópolo, MG
Kohanoff, J
Lynden-Bell, RM
机构
[1] Queens Univ Belfast, Sch Math & Phys, Atomist Simulat Ctr, Belfast BT7 1NN, Antrim, North Ireland
[2] Univ Cambridge, Chem Lab, Cambridge CB2 1EW, England
基金
英国工程与自然科学研究理事会;
关键词
D O I
10.1021/jp0602326
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Ab initio simulations of a single molecule of HCl in liquid dimethyl imidazolium chloride [dmim][Cl] show that the acidic proton exists as a symmetric, linear ClHCl- species. Details of the solvation structure around this molecule are given. The proton-transfer process was investigated by applying a force along the antisymmetric stretch coordinate until the molecule broke. Changes in the free energy and local solvation structure during this process were investigated. In the reaction mechanism identified, a free chloride approaches the proton from the side. As the original ClHCl- distorts and the incoming chloride forms a new bond to the proton, one of the original chlorine atoms is expelled and a new linear molecule is formed.
引用
收藏
页码:8798 / 8803
页数:6
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