物理化学学报Issue(7)：1223-1229,7.DOI:10.3866/PKU.WHXB201405091
碱金属掺杂叔丁基杯[4]芳烃体系的结构及非线性光学性质
Structures and Nonlinear Optical Properties of Alkali Metal-Doped t-Bu-calix[4]arene Molecules
摘要
Abstract
Using density functional theory with the B3LYP functional, the optimized geometrical structures of the M@t-Bu-calix[4]arene and (M@t-Bu-calix[4]arene)Li′(M=Li, Na, K) compounds were obtained. Five stable isomers were identified for each bi-alkali-metal-doped (M@t-Bu-calix[4]arene)Li′species. The first three low-lying isomers have considerable intramolecular interaction energies between alkali metal atoms and the t-Bu-calix[4]arene molecule, indicating their stabilities. According to natural bond orbital analyses, the outside Li′atom is negatively charged in some (M@t-Bu-calix[4]arene)Li′structures, indicating the alkalide characteristics of these isomers. In addition, the nonlinear optical (NLO) properties of isolated and alkali-metal-doped t-Bu-calix [4]arene molecules were calculated using the CAM-B3LYP method. The results indicate that the single-doped effect of alkali metal M greatly enhances the first hyperpolarizability (β0) of the t-Bu-calix[4]arene molecule. In particular, when another Li atom is doped outside the M@t-Bu-calix[4]arene species, the resulting (M@t-Bu-calix[4]arene)Li′compounds exhibit largerβ0 values. Obviously, the alkali-metal-doping effect plays a crucial role. The MLi′-4 conformation has the largestβ0 value (41827-114354 a.u.) among al the (M@t-Bu-calix[4]arene) Li′structural isomers, and it is found that theβ0 value of (M@t-Bu-calix[4]arene)Li′gradually increases with increasing atomic number of the alkali metal M. Therefore, alkali-metal doping is an effective approach to enhance the NLO response of the t-Bu-calix[4]arene molecule.关键词
密度泛函理论/掺杂效应/碱金属化物/非线性光学/一阶超极化率Key words
Density functional theory/Doping effect/Alkalide/Nonlinear optics/First hyperpolarizability分类
化学化工引用本文复制引用
侯娜,李莹,吴迪,李志儒..碱金属掺杂叔丁基杯[4]芳烃体系的结构及非线性光学性质[J].物理化学学报,2014,(7):1223-1229,7.基金项目
The project was supported by the National Natural Science Foundation of China (21173095,21173098,21303066).国家自然科学基金(21173095,21173098,21303066)资助项目 （21173095,21173098,21303066）
