Photoelectron Velocity Map Imaging Spectroscopic and Theoretical Study of Heteronuclear MNi(CO) 7 – (M = V, Nb, Ta)

作者：Jumei Zhang, Gang Li, Qinqin Yuan, Jinghan Zou, Dong Yang, Huijun Zheng, Chong Wang, Jianpeng Yang, Qiangshan Jing, Yan‐Ming Liu, Hongjun Fan, Hua Xie · 发表于：The Journal of Physical Chemistry A · 年份：2020 · DOI：10.1021/acs.jpca.0c00313 · 被引用次数：11 · 研究领域：Advanced Chemical Physics Studies、Catalytic Processes in Materials Science、Molecular Junctions and Nanostructures

A series of heteronuclear group 5 metal–nickel carbonyls MNi(CO) 7 – (M = V, Nb, Ta) have been generated via a laser ablation ion source and studied by photoelectron velocity-map imaging spectroscopy. Quantum chemical calculations have been performed to probe the electronic and geometric structures and help to assign the spectra. The adiabatic detachment energies (ADEs) and vertical detachment energies (VDEs) are deduced from spectra to be 3.40/3.58, 3.34/3.55, 3.30/3.50 eV, which are consistent with quantum chemical computational results. The MNi(CO) 7 – (M = V, Nb, Ta) consists of three bridging carbonyls, one carbonyl terminally bonded to the Ni atom and three carbonyls terminally bonded to the M (M = V, Nb, Ta) atom. These geometries are different from homobinuclear Cr 2 (CO) 7 +, Ni 2 (CO) 7 +, Pd 2 (CO) 7 +, and Fe 2 (CO) 7 – and heterobinuclear CuFe(CO) 7 –, CoZn(CO) 7 +, and CO is largely activated by a bridging coordination mode. The experimental and theoretical results would provide important information to understand the chemisorbed CO molecules on alloy surfaces or interfaces, which is of great significance to elucidate CO molecule activation processes.