Web Release Date: October 21,
Photoelectron Spectroscopy of Free Polyoxoanions Mo6O192- and W6O192- in the Gas Phase
and
Department of Physics, Washington State University, 2710 University Drive, Richland, Washington 99352, Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352, School of Chemistry, The University of Melbourne, Parkville, Victoria 3010, Australia, and Department of Chemistry, University of Alabama, Tuscaloosa, Alabama 35487
Received: June 4, 2004
In Final Form: August 12, 2004
Abstract:
Two doubly charged polyoxoanions, Mo6O192- and W6O192-, were observed in the gas phase using electrospray ionization. Their electronic structures were investigated using photoelectron spectroscopy and density functional calculations with relativistic effective core potentials. Each dianion was found to be highly stable despite the presence of strong intramolecular Coulomb repulsion, estimated to be about 2 eV for each system. The valence detachment features were all shown to originate from electronic excitations involving oxygen lone-pair type orbitals. Their observed energies were in excellent agreement with the theoretical vertical detachment energies calculated using time-dependent density functional theory. Despite being multiply charged, polyoxometalate oxide clusters can be studied in the gas phase, providing the opportunity for detailed benchmark theoretical studies on the electronic structures of these important transition-metal oxide systems.
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