Density functional theory （DFT） calculations are employed to investigate the structural and electronic properties of MoS6^- and MoS6 clusters. Generalized Koopmans＇ theorem is applied to predict the vertical detach...Density functional theory （DFT） calculations are employed to investigate the structural and electronic properties of MoS6^- and MoS6 clusters. Generalized Koopmans＇ theorem is applied to predict the vertical detachment energies and simulate the photoelectron spectra （PES）. Intriguingly, the terminal S2-, polysulfide S2^2- and S3^2- ligands simultaneously emerge in the lowest-energy structure of MoS6. Molecular orbital analyses are performed to analyze the chemical bonding in MoS6^-/0 clusters and elucidate their structural and electronic properties.展开更多
Density functional theory（DFT） and coupled cluster theory（CCSD（T）） calculations were employed to investigate the structural and electronic properties of Nb S6^- and Nb S6 clusters. Generalized Koopmans＇ theorem...Density functional theory（DFT） and coupled cluster theory（CCSD（T）） calculations were employed to investigate the structural and electronic properties of Nb S6^- and Nb S6 clusters. Generalized Koopmans＇ theorem was applied to predict the vertical detachment energies and simulate the photoelectron spectra（PES）. The current study indicated that various types of sulfur ligands（i.e., S^（2-）, S^（2-）, S2^（2-） and S3^（2-）） were presented in the lowest-energy structures of Nb S6^（-/0）. The ground-state structure of Nb S6^- is shown to be Cs（~1A＇） symmetry with a terminal S^（2-）, a side-on bound S2^（2-） and a S3^（2-） ligands. Molecular orbital analyses were performed to analyze the chemical bonding in NbS6^（-/0） clusters and elucidate their structural and electronic properties.展开更多
Reaction of (NH 4) 2MoS 4 with [Cu(MeCN) 4](BF 4) and (n-Bu) 4NBr in CH 2Cl 2 afforded a new hexanuclear cluster [(n-Bu) 4N] 3[MoS 4Cu 5Br 6] (1). 1 crystallizes in the monoclinic system, space group P2 ...Reaction of (NH 4) 2MoS 4 with [Cu(MeCN) 4](BF 4) and (n-Bu) 4NBr in CH 2Cl 2 afforded a new hexanuclear cluster [(n-Bu) 4N] 3[MoS 4Cu 5Br 6] (1). 1 crystallizes in the monoclinic system, space group P2 1/c, with lattice parameters a=1.17383(4) nm, b=2.40136(4) nm, c=2.64112(5) nm, β=94.2020(5)°, V=7.4247(5) nm 3 and Z=4. The structure of the [MoS 4Cu 5Br 6] 3- trianion of 1 is composed of one nido-like [MoS 3Cu 3] core and one half-open cubane-like [MoS 3Cu 3Br] core, which are interconnected by sharing the same MoSCuS plane. The Mo...Cu distances vary in the range of 0.2622(6)-0.2692(5) nm.展开更多
基金Supported by the National Natural Science Foundation of China (21171039, 21073035, 21071031 and 90922022)National Science Foundation for Fostering Talents in Basic Research of the National Natural Science Foundation of China (J1103303)Foundation of Fuzhou University (0460-022342 and 0041-600616)
文摘Density functional theory （DFT） calculations are employed to investigate the structural and electronic properties of MoS6^- and MoS6 clusters. Generalized Koopmans＇ theorem is applied to predict the vertical detachment energies and simulate the photoelectron spectra （PES）. Intriguingly, the terminal S2-, polysulfide S2^2- and S3^2- ligands simultaneously emerge in the lowest-energy structure of MoS6. Molecular orbital analyses are performed to analyze the chemical bonding in MoS6^-/0 clusters and elucidate their structural and electronic properties.
基金supported by the National Natural Science Foundation of China(21301030,21371034 and 21373048)the Natural Science Foundation of Fujian Province for Distinguished Young Investigator(2013J06004)Foundation of Fuzhou University(2012-XY-6)
文摘Density functional theory（DFT） and coupled cluster theory（CCSD（T）） calculations were employed to investigate the structural and electronic properties of Nb S6^- and Nb S6 clusters. Generalized Koopmans＇ theorem was applied to predict the vertical detachment energies and simulate the photoelectron spectra（PES）. The current study indicated that various types of sulfur ligands（i.e., S^（2-）, S^（2-）, S2^（2-） and S3^（2-）） were presented in the lowest-energy structures of Nb S6^（-/0）. The ground-state structure of Nb S6^- is shown to be Cs（~1A＇） symmetry with a terminal S^（2-）, a side-on bound S2^（2-） and a S3^（2-） ligands. Molecular orbital analyses were performed to analyze the chemical bonding in NbS6^（-/0） clusters and elucidate their structural and electronic properties.
基金theKeyLaboratoryofOrganicChemistryofJiangsuProvince (No .KJS0 1017)andtheStateKeyLaboratoryofCoordinationChemistryofNanjingUniversity
文摘Reaction of (NH 4) 2MoS 4 with [Cu(MeCN) 4](BF 4) and (n-Bu) 4NBr in CH 2Cl 2 afforded a new hexanuclear cluster [(n-Bu) 4N] 3[MoS 4Cu 5Br 6] (1). 1 crystallizes in the monoclinic system, space group P2 1/c, with lattice parameters a=1.17383(4) nm, b=2.40136(4) nm, c=2.64112(5) nm, β=94.2020(5)°, V=7.4247(5) nm 3 and Z=4. The structure of the [MoS 4Cu 5Br 6] 3- trianion of 1 is composed of one nido-like [MoS 3Cu 3] core and one half-open cubane-like [MoS 3Cu 3Br] core, which are interconnected by sharing the same MoSCuS plane. The Mo...Cu distances vary in the range of 0.2622(6)-0.2692(5) nm.
