OH^-(H2O)n(n=1~8)团簇的量子化学研究  

Study of OH^-(H2O)n(n=1~8)clusters by quantum chemistry

作　　者：杨忠志[1] 石华[1,2] 刘翠 YANG Zhongzhi;SHI Hua;LIU Cui(School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, China;School of Marine Science and Environment, Dalian Ocean University, Dalian 116023, China)

机构地区：[1]辽宁师范大学化学化工学院,辽宁大连116029 [2]大连海洋大学海洋科技与环境学院,辽宁大连116023

出　　处：《辽宁师范大学学报（自然科学版）》2020年第2期193-203,共11页Journal of Liaoning Normal University:Natural Science Edition

基　　金：国家自然科学基金资助项目(21133005,21473083,21603091)。

摘　　要：分别在B3LYP/6-31++G(d,p)、MP2/6-31++G(d,p)、MP2/aug-cc-pVDZ水平下,对OH-(H2O)n(n=1~8)团簇进行结构、二阶稳定化能、结合能等性质的研究,并进行电荷性质讨论,分析了上述稳定构象下的电荷分布和电荷转移.计算结果表明:对于氢氧根离子水团簇的结构、电荷转移、二阶稳定化能、结合能等性质,3种方法的计算结果多数比较接近,且氢氧根离子水团簇的结构、电荷转移、二阶稳定化能都与氢氧根离子的氧原子的配位数有关.OH-与第一壳层水分子形成的平均氢键长R-O…H,随着OH-氧的配位数的增加而增加.对于水分子数相同的团簇,第一壳层的平均角度θ-H…O…H、氢氧根离子总电荷与第一壳层水分子平均电荷的乘积qOH-×q-FW、氢氧根离子的电荷转移量的绝对值|ΔqOH-|以及第一壳层的平均二阶稳定化能E-ave(O…H)随配位数的增加而减小.The structures,second-order stabilization energies,and binding energies of the OH-(H2O)n(n=1~8)clusters were studied at B3LYP/6-31++G(d,p),MP2/6-31++G(d,p),and MP2/aug-cc-pVDZ levels,respectively.The charge distributions and charge transfer of these stable conformations also were discussed.The calculation results show that the results of the structures,charge transfer,second-order stabilization energies,and binding energies from these three methods are mostly close.In addition,the structures,charge transfer,and second-order stabilization energies of OH-(H2O)n clusters are related to the coordination number of OH-.For example,the average hydrogen bond length formed by OH-and its first shell water molecules,R-O…H,increases with the increasing coordination number.The average angle between two neighboring hydrogen bonds in the first shell,θ-H…O…H,the product of the net charge of OH-and average charge of the first-shell water molecules,qOH-×q-FW,the absolute value of charge transfer of OH-,ΔqOH-,and the average second-order stabilization energy between OH-and its first-shell water molecules,E-ave(O…H),decrease with the increasing coordination number for the clusters with the same number of water molecules.

关 键 词：氢氧根离子水团簇 配位数 电荷转移 二阶稳定化能 结合能 

分 类 号：O641.121[理学—物理化学]