Zhang Jumei, Xie Hua, Li Gang, Kong Xiangtao, Fan Hongjun, Jiang Ling
State Key Laboratory of Molecular Reaction Dynamics, Collaborative Innovation Center of Chemistry for Energy and Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Sciences , 457 Zhongshan Road, Dalian 116023, China.
University of Chinese Academy of Sciences , 19A Yuquan Road, Beijing 100049, China.
J Phys Chem A. 2018 Jan 11;122(1):53-59. doi: 10.1021/acs.jpca.7b09230. Epub 2017 Dec 27.
Photoelectron velocity-map imaging spectroscopy was conducted for the heterotrinuclear metal carbonyls VNi(CO) (n = 6-10). Electronic structure calculations were performed to understand the experimental spectral features. The binding motif of a V-V-Ni chain with two side-on-bonded carbonyls and two bridging carbonyls is favored in the n = 6-9 clusters. A VNi triangle core structure is formed at n = 10 with the involvement of two carbonyls with the carbon atom triply coordinated to metal atoms, three bridging carbonyls, and five terminal carbonyls, in which CO bonding configurations mirror the adsorption features in the three-fold hollow, bridging, and atop sites on the closely packed surface, respectively. The present study provides a stepwise picture for molecular level understanding of CO bonding on heteronuclear metal clusters, which is directly relevant to the elementary processes of CO on the alloy surfaces/interfaces.
对异核金属羰基化合物VNi(CO)（n = 6 - 10）进行了光电子速度映射成像光谱研究。进行了电子结构计算以理解实验光谱特征。在n = 6 - 9的簇中，具有两个侧基配位羰基和两个桥连羰基的V - V - Ni链的键合模式更受青睐。在n = 10时形成了一个VNi三角形核心结构，其中涉及两个羰基，碳原子与金属原子三重配位，三个桥连羰基和五个端基羰基，其中CO的键合构型分别反映了在紧密堆积表面上的三重空心、桥连和顶位的吸附特征。本研究为在分子水平上理解异核金属簇上的CO键合提供了一个逐步的图景，这与合金表面/界面上CO的基本过程直接相关。
