碱金属阳离子M^+的引入及质子化对[V_(12)O_(32)]^(4-)二阶非线性光学性质影响的密度泛函理论研究  

Density Functional Theory Studies on the Second-order Nonlinear Optical Properties of [V_(12)O_(32)]^(4-)and Its Alkali Metal Cation and Protonated Derivatives

作　　者：林燕[1] 张婷[1] 颜力楷[1] 苏忠民[1] 

机构地区：[1]东北师范大学化学学院功能材料化学研究所,长春130024

出　　处：《高等学校化学学报》2013年第3期615-620,共6页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20971020和21073030);教育部新世纪优秀人才计划(批准号:NCET-10-318);吉林省科技发展计划项目(批准号:20100320)资助

摘　　要：采用密度泛函理论(DFT)方法研究了碗状钒多酸阴离子[V12O32]4-、其碱金属阳离子衍生物[V12O32M]3-(M=Li,Na,K)及质子化衍生物的几何结构和二阶非线性光学(NLO)性质.结果表明,碱金属阳离子M+的引入对体系的几何结构和第一超极化率(β0)影响很小;而质子化的位置和取向对体系的几何结构和第一超极化率均有较大影响,与钒多酸阴离子[V12O32]4-相比,碗中部桥氧质子化体系的β0值增大,且比碗口处及碗底处桥氧质子化体系的β0值大270～400 a.u.The geometrical structures and second-order nonlinear optical（NLO）properties of [V12O32]4-,[V12O32M]3-（M=Li＋,Na＋,K＋） and the protonated derivatives were investigated via density functional theory（DFT） method.The results show that the alkali metal cation M＋ has little effect on the geometrical structure of the system and the first hyperpolarizability（β0）.However,the different positions and different orientations of the protons have different impact on β0 values.Compared with [V12O32]4-,the β0 values of the protonated systems,in which the middle bridging oxygen atoms are protonated,increase significantly.Besides,when the middle bridging oxygen atoms are protonated,meanwhile the protons point to inside of the bowl,this complex exhibits the largest β0 value.

关 键 词：钒多酸阴离子 非线性光学性质 质子化 密度泛函理论 

分 类 号：O641[理学—物理化学]