C_(60)PY/TTF(BEDT-TTF)衍生物的电子结构及二阶非线性光学性质的理论研究  

Theoretical investigation on electronic spectra and second-order nonlinear optical properties of substituted fulleropyrrolidine tetrathiafulvalene derivatives

作　　者：朱玉兰[1] 阚玉和[1] 苏忠民[2] 周子彦[3] 仇永清[2] 段雪梅[2] 封继康[4] 

机构地区：[1]淮阴师范学院化学系,江苏淮安223001 [2]东北师范大学化学学院功能材料化学研究所,吉林长春130024 [3]延边大学理工学院化学系,吉林延吉133002 [4]吉林大学理论化学研究所理论化学计算国家重点实验室,吉林长春130023

出　　处：《分子科学学报》2002年第4期204-210,共7页Journal of Molecular Science

基　　金：国家自然科学基金资助项目(20162005)

摘　　要：　用AM1和INDO/CI方法,计算了系列N-甲基-吡咯烷[3,4]C60四硫富瓦烯(C60PY/TTF)的结构和电子光谱,计算结果和实验结果一致.在正确光谱的基础上,用ZINDO/CI-SOS公式计算了该系列分子的二阶非线性光学系数,分析了其分子轨道成分.结果表明,在未占有轨道电子云主要来自C60的贡献,而最高占有轨道的电子云主要集中在TTF上.The electronic spectroscopic properties and second-order NLO coefficient β were obtained by using the approach of ZINDO/S single exited configuration interaction(SCI) based on the AM1 geometries of a series of the N-methyl-pyrrolidinofullerene /tetrathiafulvalenyl(C60PY/TTF) and N-methyl-pyrrolidinofullerene bis(ethylenedithio)-tetrathiafulvalene(C60PY/BEDT-TTF)dyads.The results suggested that the calculated electronic spectra the studied molecule were consistent well with those from the experiment.With the increase of the conjugation vinyl length,β values became large.And the orbital component was analyzed.It was found that the electron cloud on unoccupied frontier orbitals mainly came from the contribution of C60 fragment,while the electron cloud on occupied frontier orbitals concentrated at TTF fragment.

关 键 词：C60PY/TTF C60吡咯烷衍生物 电子光谱 二阶非线性光学性质 电荷转移 电子结构 INDO/CI AM1 富勒烯 

分 类 号：O635.1[理学—高分子化学] O641.[理学—化学]