期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：1977
卷号：74
期号：8
页码：3109-3113
DOI：10.1073/pnas.74.8.3109
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：Using the SCF-X-SW method the ground state electronic structures of (HO)3Mo{equiv}Mo(OH)3, (H2N)3Mo{equiv}Mo(NH2)3, and (Me2N)3Mo{equiv}Mo(NMe2) have been calculated. The results provide a detailed description of the metal-to-metal triple bonds present; some of the more important molecular orbitals are shown in detail as contour diagrams. The energy levels of all filled valence shell/molecular orbitals and the lower virtual orbitals are presented in diagrams. The {pi}(eu) and {sigma}(a1g) orbitals which have large amounts of metal character can be identified as the orbitals primarily responsible for Mo-Mo bonding. Using the transition state technique to allow for relaxation effects, the photoelectron spectra (up to 12 eV) have been calculated for Mo2(OH)6 and Mo2(NH2)6 and found to compare very well, after applying a constant downshift to correct for inductive effects, with experimental spectra for Mo2[OCH2C(CH3)3]6 and Mo2[N(CH3)2]6. The experimental photoelectron spectra are reported.
