含有金属-金属键的双核原子簇离子体系[Mo_2S_n]^(2-)(n=6～9)的电子结构与电子光谱

Electronic Structure and Electronic Spectra of the Dinuclear Cluster Anions, [Mo_2Sn]^(2-)(n=6～9) with Metal-Metal Bond

使用SCF-CI方法研究了含有Mo—Mo单键的原子簇离子体系[Mo_2Sn]^(2-)(n=6～9)的电子结构及电子光谱。讨论了随n增加,配体S,S_2,S_4对Mo—Mo键序、原子电荷的影响及其变化规律。分析了原子簇离子中的d-d相互作用能级次序及Mo—Mo,Mo—S′_t等键的性质,CI计算得到的谱带波数及强度次序与实验符合。指认分析表明,谱带的跃迁性质是有趣的,如第一吸收带为成键轨道之间的跃迁σ_(x^2-y^2)→π_(xz)(n=6～8),同时,对电子跃迁的性质进行了分类,对谱带的电荷转移性质也进行了讨论。

The electronic structure and electronic spectra of [Me_2S_n]~2-(n=6～9)with Mo—Mo single bond are studied by SCF-CI. The changes of Mo—Mo bond order and atomic charges with n increasing are discussed. The unusual sequence of d-d interactions in the cluster anions and the nature of some bonds (Mo—Mo, Mo—S'_t) are analyzed.The calculated values of wave number and transition intensity of the spectra correspond with the experimental results.The bands are assigned and the properties of their charge transfer are discussed. In addition, some transitions are interesting, for instance, the transition between bonding orbitals, σ_(y_-y^2)→π_.