title: Theoretical study of the pseudo-Jahn-Teller effect in the edge-sharing bioctahedral complex Mo(2)(DXylF)(2)(O(2)CCH(3))(2)(mu(2)-O)(2).
abstract: A study of the D(2h) to C(2h) pseudo-Jahn-Teller distortion in the edge-sharing bioctahedral complex Mo(2)(DXylF)(2)(O(2)CCH(3))(2)(mu(2)-O)(2) is presented. We have performed extensive density functional theory (DFT) and complete active space self-consistent field (CASSCF) calculations. For both the full target complex and a model derived by replacing xylyl and methyl groups with hydrogens we observe that the central Mo(2)(mu(2)-O)(2) motif displays C(2h) rather than D(2h) symmetry. Analytical CASSCF frequency calculations prove that the rhomboidal distortion of the complex from D(2h) to C(2h) is due to a vibronic mixing of the ground electronic state and a low-lying pidelta* excited state.
authors.affiliation: School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh, Scotland, EH14 4AS.
authors.forename: Justyna M
authors.initials: JM
authors.lastname: Zurek
authors.forename: Martin J
authors.initials: MJ
authors.lastname: Paterson
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D008982:Molybdenum / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D056831:Coordination Complexes; D008982:Molybdenum