Me_nCH_(3-n)O^-溶剂化自由能和Me_nCH_(3-n)OH(n=0,1,2,3)在水溶液中酸性次序翻转的理论研究:离散-连续组合模型  

Studies of Solvation Free Energies of Me_n CH_(3-n)O^-and the Inversion of the Acidity Scale of Me_n CH_(3-n)OH(n=0,1,2,3) in Aqueous Solution by a Combined Discrete-continuum Model

作　　者：曹志霁[1] 莫亦荣[1,2] 林梦海[1] 张乾二[1] 

机构地区：[1]厦门大学化学系固体表面物理化学国家重点实验室,理论化学研究中心,福建厦门361005 [2]西密执安大学化学系,美国密执安49008

出　　处：《厦门大学学报（自然科学版）》2005年第3期373-376,共4页Journal of Xiamen University：Natural Science

基　　金：国家自然科学基金 ( 90206038;20373053 );福建省重大项目基金(2002F010)资助

摘　　要：采用离散连续组合模型计算了MenCH3-nO- (n=0, 1, 2, 3)在水溶液中的溶剂化自由能.结果表明,采用离散连续组合模型计算的溶剂化能正确反映出了甲醇类在水溶液中的酸性次序,尽管存在较大的误差,但其同样表现为一整体的偏差.此外基于离散连续组合模型可以发现,溶剂效应短程作用和长程作用对甲醇类由气态到水溶液中次序变化均起着重要作用.The solvation free energies of Me_nCH_(3-n)O^- with n=0,1,2 and 3,have been computed by means of a combined discrete-continuum model.The results show that the combined discrete-continuum model is a small standard deviation for the average error,although its absolute errors are larger than ones of continuum model.Based on the computed solvation free energies,we further explore the nature of the irregular order in acidity of a series of methyl-substituted alcohols in aqueous solution.Analyses reveal that both short-range and long-range solute-solvent interactions play important role in the inversion of acidity.

关 键 词：溶剂化自由能 组合模型 水溶液 离散 理论研究 中酸性 翻转 模型计算 溶剂化能 长程作用 溶剂效应 醇类 偏差 气态 

分 类 号：O613.61[理学—无机化学] TV698.11[理学—化学]