论文部分内容阅读
采用从头计算MP2方法和密度泛函理论方法,对过渡金属团簇[PdAu8(PR3)8]2+(R=Me,OMe,H,F,Cl,CN)何结构、电子结构以及团簇各组成部分之间的结合能进行了研究.MP2方法和SVWN局域泛函能够对团簇的结构准确的描述,而离域泛函BP86,PBE,BLYP和杂化泛函B3LYP则过高地估计了团簇的几何结构参数.电子结构研明Pd,Au原子通过d电子的成键作用构成团簇内核[PdAu8]2+,[PdAu8]2+与PR3配体则通过“σ给予/π反馈”模式PR3配体与[PdAu8]2+的结合能够加强Pd-Au之间的成键作用,增大前线轨道能级间隙,从而提高团簇的稳定性.P体中R基团供、吸电能力的变化对[PdAu8(PR3)8]2+结构的影响较小,但对[PdAu8]2+-PR3结合能的影响较大.能量显示不同PR3与[PdAu8]2+之间具有相近的轨道作用能,与R基团供、吸电能力相关的非轨道作用能成为影响两者牢固程度的决定因素.
The structure, electronic structure, and cluster of transition metal cluster [PdAu8 (PR3) 8] 2+ (R = Me, OMe, H, F, Cl, CN) were studied by using ab initio MP2 method and density functional theory The binding energy between the components can be studied. The MP2 method and the SVWN local function can accurately describe the structure of the clusters, while the BP86, PBE, BLYP and B3LYP are overestimated The structure of PdAu8 2 + and Pd3 + ligands are described by “σ / π feedback ”Combination of PR3 ligand with [PdAu8] 2+ can enhance the bonding between Pd-Au and increase the gap of frontier orbital energy level to improve the stability of the cluster.In the P body, The changes in the capacity of the PdAu8 (PR3) 8] 2+ showed a small effect on the binding energy of [PdAu8] 2 + -PR3, but the energy showed a significant difference between the different PR3 and [PdAu8] 2+ Similar orbital energy, non-orbital effects associated with the ability of the R groups to supply and sink can become the determinants of the firmness of both.