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dc.contributor.authorStoyanov, Stanislav R.
dc.contributor.authorVillegas, John M.
dc.contributor.authorRillema, D. Paul
dc.identifier.citationStoyanov, Stanislav R.; Villegas, John M.; Rillema, D. Paul. 2004. Spectroscopic Properties of [Pt2(μ-P2O5H2)4]:4- A Time-Dependent Density Functional Theory and Conductor-like Polarizable Continuum Model Investigation. The Journal of Physical Chemistry B, v.108 no.32 pp.12175-12180en_US
dc.descriptionClick on the DOI link to access the article (may not be free)en_US
dc.description.abstractThe calculation of the singlet ground-state (SGS) and the lowest-lying triplet-state (LLTS) geometries of [Pt2(μ-P2O5H2)4]4- in the gas phase using density functional theory (DFT) produces 7% Pt−Pt bond shortening in the LLTS as compared to SGS. The transition from the Pt−Pt antibonding HOMO to the bonding LUMO+1 in the gas phase and to the bonding LUMO in water creates a metal−metal σ bond in both excited states. According to the molecular orbital population analysis in water performed using the conductor-like polarizable continuum model (CPCM) and the SGS geometry, the Pt−Pt bond arises from the overlap of the metal p orbitals. The singlet excited-state energy of 27 240 cm-1 in the gas phase is only 40 cm-1 higher than the experimental absorption energy. The first triplet excited-state energy of 22 730 cm-1 in the gas phase and 22 810 cm-1 in water correlates with the experimental phosphorescence excitation energy of 22 100 cm-1. The energy of the LLTS correlates with the experimental phosphorescence emission energy.en_US
dc.description.sponsorshipWe acknowledge the support of Kansas NSF Cooperative Agreement EPS 987432, the Wichita State University High Performance Computing Center, the Wichita State University Office of Research Administration, the Department of Energy, and Parker Fellowships (S.R.S. and J.M.V.). We also thank Dr. David M. Eichhorn for helping us to access the Inorganic Crystal Structure Database.en_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.ispartofseriesThe Journal of Physical Chemistry B;v.108 no.32
dc.titleSpectroscopic Properties of [Pt2(μ-P2O5H2)4]:4- A Time-Dependent Density Functional Theory and Conductor-like Polarizable Continuum Model Investigationen_US
dc.description.versionPeer reviewed
dc.rights.holderCopyright © 2004, American Chemical Society

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