Department of Chemistry, Fuzhou University, Fuzhou, Fujian 350108, P. R. China.
J Phys Chem A. 2013 Jul 11;117(27):5632-41. doi: 10.1021/jp309163c. Epub 2013 Jun 27.
Density functional theory (DFT) and coupled cluster theory (CCSD(T)) calculations are carried out to investigate the electronic and structural properties of a series of monomolybdenum sulfide clusters, MoSn(-/0) (n = 1-5). Generalized Koopmans' theorem is applied to predict the vertical detachment energies and simulate the photoelectron spectra (PES). We found that the additional sulfur atoms have a tendency to successively occupy the terminal sites in the sequential sulfidation until the Mo reaches its maximum oxidation sate of +6. After that, the polysulfide ligands (viz., S2 and S3) emerge in the MoS4 and MoS5(-/0) clusters. The MoS4 (C2, (1)A) is predicted to be the ground state and may be used as a neutral model for the sulfur-rich edge sites of the fresh MoS2 catalysts. Molecular orbital analyses are performed to analyze the chemical bonding in the monomolybdenum sulfide clusters and to elucidate their electronic and structural evolution.
密度泛函理论(DFT)和耦合簇理论(CCSD(T))计算被用来研究一系列单钼硫化物簇，MoSn(-/0) (n = 1-5)的电子和结构性质。广义 Koopmans 定理被应用于预测垂直离化能和模拟光电子能谱(PES)。我们发现，额外的硫原子倾向于连续占据端基位置，直到钼达到其最大氧化态+6。之后，多硫化物配体（即 S2 和 S3）出现在 MoS4 和 MoS5(-/0)簇中。MoS4 (C2, (1)A) 被预测为基态，可作为富含硫的新鲜 MoS2 催化剂边缘位点的中性模型。分子轨道分析被用来分析单钼硫化物簇中的化学键，并阐明它们的电子和结构演变。
