电子化物Li_3@calix[4]pyrrole和Li_3O@calix[4]pyrrole的结构及非线性光学性质的理论研究  

Theoretical Studies on Structures and Nonlinear Optical Properties of Superalkali-based Electrides Li_3@calix[4]pyrrole and Li_3O@calix[4]pyrrole

作　　者：侯娜[1] 李莹[1] 吴迪[1] 李志儒[1] 

机构地区：[1]吉林大学理论化学研究所,理论化学计算国家重点实验室,长春130023

出　　处：《高等学校化学学报》2014年第4期798-803,共6页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21173095;21173098;21303066)资助~~

摘　　要：对超碱金属电子化物Li3@calix[4]pyrrole和Li3O@calix[4]pyrrole的几何结构、相对稳定性和非线性光学性质进行了理论研究.2个体系分别含有4个和2个稳定异构体.通过与Li@calix[4]pyrrole比较发现,以超碱金属Li3和Li3O为电子供体可以给体系带来更大的非线性光学响应.当Li3和Li3O分子平面与calix[4]pyrrole配体的4个N原子构成的平面平行作用时,超碱金属的电离程度更高,体系具有更大的一阶超极化率值.The geometrical structures, relative stabilities and nonlinear optical properties of superalkali-based electrides Li3@calix[4]pyrrole and Li3O@calix[4]pyrrole were studied in theory. Four and two isomers were identified for Li3@calix[4]pyrrole and Li3O@calix[4]pyrrole, respectively. The results show that, replacing alkali metal with superalkalis brings larger NLO responses to the electrides. In addition, the Li3 and Li3 O molecules are ionized to a greater degree when they are parallel to the plane composed by four N atoms of the calix[4]pyrrole complexant. As a result, such structures exhibit larger first hyperpolarizabilities（β0） than the other isomers.

关 键 词：电子化物 密度泛函理论 超碱金属 一阶超极化率 非线性光学性质 

分 类 号：O641[理学—物理化学]