H_3PAuPh与(H_3PAu)_2(1,4-C_6H_4)_2光谱性质的密度泛函研究  

Density functional theory studies on spectral properties of H_3PAuPh and(H_3PAu)_2(1,4-C_6H_4)_2

作　　者：矫玉秋[1] 赵昆[1] 卢贵武[1] 

机构地区：[1]中国石油大学数理系,北京102249

出　　处：《物理学报》2008年第3期1592-1598,共7页Acta Physica Sinica

基　　金：国家自然科学基金(批准号:50672132;60778034);教育部科学技术研究重点项目(批准号:107020)资助的课题~~

摘　　要：用密度泛函(DFT)方法优化了配合物H3PAuPh(a),(H3PAu)2(1,4-C6H4)2(b)的基态的几何结构,并用含时密度泛函方法计算了它们的吸收光谱.结果表明配合物a与b的最低能量吸收谱线的波长分别为257.5nm和307.6nm,皆具有C(2p)→Au(6p)电荷转移参与下的pπ(芳环)→pπ*(芳环)跃迁本质,并伴有Au(5d)→Au(6p)的金属中心电荷转移性质.配合物b是由两个配合物a相连接而成,配合物b的分子轨道也是由配合物a的分子轨道组合而成.由于轨道组合中存在pπ*或pπ相互作用,配合物b的最低能量吸收谱线的波长大于配合物a的相应值.The structures of the H3 PAuPh and （H3 PAu）2 （1,4-C6 H4 ）2 are optimized using the density functional theory for the ground states. The lowest-energy absorption spectra are calculated by the time-dependent density functional theory, and it is found that the 257.5nm line arises from 1 ^A′→1 A′ transition for H3 PAuPh and the 307.6nm line arises from 1^ A→1^ A transition for （H3PAu）2 （1,4-C6H4 ）2- The lowest-energy absorption spectra of the Au complexes have the nature of pπ （aromatic-nucleus） → pπ^＊ （aromatic-nucleus） C（2p）→Au（6p） charge transfer which is accompanied by Au（5d）→Au（6p） transition character. The （ H3 PAu）2 （ 1,4-C6 H4 ）2 is approximately made up of double H3 PAuPh. So the molecular orbitals of （ H3 PAu）2 （ 1,4-C6 H4 ）2 can be regarded as the compounding of the molecular orbitals of H3PAuPh. The compounding of the molecular orbitals with the reciprocities of pπ^＊ or pπ makes the lowest-energy absorption energy of （H3 PAu）2 （1,4-C6H4）2 lower than that of H3PAuPh.

关 键 词：激发态 光谱 密度泛函 AuPH3 配合物 金 

分 类 号：O561.3[理学—原子与分子物理]