Theoretical Investigations on the NbMoS6-/0 Clusters
作者单位：Department of Chemistry Fuzhou University
会议名称：《中国化学会第30届学术年会-第十八分会：电子结构理论方法的发展与应用》
会议日期：2016年
学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学]
基 金：supports from the National Natural Science Foundation of China (21301030, 21371034 and 21373048) Foundation of Fuzhou University (2012-XY-6)
关 键 词：Density Functional Theory Metallic Sulfide Clusters Simulated Photoelectron Spectrum
摘 要：Through an extensive literature survey, we found that transition metal sulfides such as molybdenum sulfides and niobium sulfides have a lot of advantages and the widespread application. In particular, molybdenum sulfides have been used as efficient catalysts in hydrodesulfurization(HDS) and hydrodenitrogenation(HDN). In the current work, we carried out an extensive computational investigation of the structural and electronic properties of heteronuclear metallic sulfide clusters NbMoS via B3LYP density functional theory(DFT) and coupled cluster [CCSD(T)] theory. Our study reveals that the ground-state of neutral NbMoS is the doublet(C A’) with two terminal S atoms, two bridging S atoms and one bridging S units(Fig. 1A). For the anionic species NbMoS, it shows disparate geometry(Fig. 1B) which is predicted to be closed-shell( C A’) with four terminal S atoms and two bridging S atoms. We found that the Nb-Mo bond length increases from 2.862 ? to 3.203 ? as one more electron is added into NbMoS. It may lead the bridging S units to be broken. The anionic photoelectron spectrum(Fig. 1C) of NbMoS was simulated based on the calculated vertical detachment energies(VDEs). The first vertical detachment energy(VDE) is calculated to be 4.69 e V using generalized Koopmans’ theorem. Molecular orbital analyses were performed to elucidate the chemical bonding in NbMoS clusters.