PH_3配体在团簇Au_(20)的顶点和面心配位的DFT理论研究  

DFT study about apex and inner coordination of PH_3 ligand on the tetrahedral gold cluster Au_(20)

作　　者：皮卫军[1] 李佳[1] 王曙光[1] 

机构地区：[1]上海交通大学化学化工学院,上海200240

出　　处：《分子科学学报》2009年第2期75-81,共7页Journal of Molecular Science

基　　金：国家自然科学基金资助项目(20573074)

摘　　要：采用DFT方法研究了在团簇Au20的顶端位点和面心位点配位PH3分子时的几何结构、电子结构以及Au—P的成键机理和能量分析.在两种配位方式下,配体PH3对团簇的几何结构影响都表现为强烈的局域形变效应.不同的配位方式下PH3与团簇的轨道作用方式不同,所形成的团簇化合物电子组态不同.两种配位方式下Au—P成键能的区别主要是来自于配体与团簇之间的Pauli排斥的不同,在面心配位时配体与团簇之间更大的Pauli排斥作用导致了该配位方式的不稳定.This paper reports geometrical and electronic structures of Au--P complexes derived from apex and inner coordination of PH3 ligand on the tetrahedral gold cluster Au20 based on DFT method. In each coordination type, there is a remarkable local geometry distortion of the gold cluster core （Au20） in the Au--P complex. On the other hand, different orbital interaction between PH3 and the cluster Au20 in two coordination types has an important effect on the electronic structure of the Au--P complex. ETS analysis results reveal that the PH3 ligand prefers to coordinate on the apex sites of the gold cluster Au20 since there is a smaller Pauli repulsion between ligand and the cluster in this coordination type.

关 键 词：团簇Au20 PH3配体 顶端配位 面心配位 DFT 

分 类 号：O641[理学—物理化学]