作　　者： ; ; ; ;

机构地区： 华南师范大学化学与环境学院

出　　处： 《物理化学学报》 2007年第4期526-530,共5页

摘　　要： 用密度泛函理论(DFT)方法在PBE0/6-31+G(d,p)水平上对乙胺、乙二胺分别与电解液中的小分子H_2O、HF分子间的相互作用进行理论计算,并在PBE/TZP水平上利用能量分解分析(EDA)方法对胺与HF、H_2O结合的II-1、II-2、III-1和III-2模型进行计算分析.结果表明,胺类物质都能与HF、H_2O形成N…H—F(O)、F(O)…H—N或F(O)…H—C的稳定氢键.但HF与胺类物质形成的氢键比H_2O与胺形成的氢键强,故胺类物质在电解液中优先稳定HF.乙二胺与HF、H_2O结合的稳定性比乙胺强.乙胺、乙二胺与HF(H2O)形成的最稳定构型均由F(O)—H…N和F(O)…H—C氢键结合形成. Intermolecular interactions between ethylamine or ethylenediamine and H2O or HF were studied theoretically using density functional theory （DFT） at the PBE0/6-31＋G（d,p） level. Natural bond orbital （NBO） analyses were employed to elucidate the hydrogen bond characteristics in these complexes. Energy decomposition analysis （EDA） method was applied to complexes of II-1, II-2, III-1, and III-2 at the PBE/TZP level. From this study, four important conclusions were drawn as follows： （1） Both HF and H2O can be stabilized by amines through N…H--F（O）, F（O）…H--N or F（O）…H--C hydrogen bonds; （2） Amines have the priority to stabilize HF, because the high electronegativies of florine atom results in the intense N--H…F hydrogen bonds; （3） Stability of the ethylenediamine-associated complexes is higher than that of ethylamine-associated complexes; （4） The most stable complexes, formed by amines with HF or H2O, include F（O）--H…N and F（O）…H-C hydrogen bonds.

关 键 词： 胺 分子间相互作用

领　　域： [理学] [理学] [理学] [理学]