苯异呃唑酮-苯多烯化合物二阶NLO性质的理论预测  

Theoretical prediction of NLO properties for phenylpolyene bridged chromo- phores with phenylisoxazolone

作　　者：阚玉和[1] 

机构地区：[1]淮阴师范学院化学系江苏省低维材料化学重点建设实验室,江苏淮安223001

出　　处：《计算机与应用化学》2005年第9期763-766,共4页Computers and Applied Chemistry

基　　金：江苏省教育厅自然科学基金资助项目(03KJD150049)

摘　　要：以量子化学半经验AM1方法优化几何构型为基础,使用INDO/CI方法对几种具有三维结构的苯异呃唑酮苯多烯及其脂环化化合物的垂直跃迁能进行了计算,同时应用完全态求和(SOS)公式计算二阶非线性光学(NLO)系数β。探讨了异构体构象、共轭烯链的长度变化及脂环化对共轭体系电子光谱和β值的影响。结果表明,顺反两类构象中,反式构象的体系具有较大的最大吸收和β值;随着共轭链长度增加,共轭程度越高,体系β值增大,λmax红移;烯链的脂环化使β值变小,而λmax 蓝移,苯异呃唑酮中苯基的空间效应对体系的电子光谱和NLO性质影响较大。The vertical transition energies of sterically stabilized phenylpolyene-bridged chromophore with phenylisoxazolone group and their alicyclic ring-locked derivatives structure were investigated with INDO/SCI method based on semi empirical method AM1 optimized geometries. The second-order nonlinear optical coefficients β were calculated according to the sum-over states （SOS） formula. In addition, the effects of conformation, chain length and alicyclic ring-locking of the designed systems on electronic spectra and β value were investigated. The results indicate that trans conformational isomer has larger λmax, and β than cis species, the higher conjugation degree and the longer of the π-conjugated bridge, the larger λmax and βλmax, blue shift and reduced β values were obtained when the polyene occurred alicyclic ring-locked. Most importantly, steric hindrance of phenyl in phenylisoxazolone has remarkable impact on λmax and β.

关 键 词：苯多烯 苯并呃唑酮 INDO/CI INDO/SOS 电子光谱 二阶非线性光学性质 

分 类 号：O624[理学—有机化学]