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dc.creatorZheldakov, I. L.en_US
dc.creatorMereshchenko, A. S.en_US
dc.creatorTarnovsky, A. N.en_US
dc.date.accessioned2010-07-12T14:01:05Z
dc.date.available2010-07-12T14:01:05Z
dc.date.issued2010en_US
dc.identifier2010-FE-02en_US
dc.identifier.urihttp://hdl.handle.net/1811/46157
dc.descriptionAuthor Institution: Bowling Green University, Department of Chemistry and Center for Photochemical Sciences, Bowling Green, Ohio 43403en_US
dc.description.abstractPhotoexcitation of hexabromoplatinate and hexabromoosmate dianions in CT and ligand field states results in remarkably fast formation (sub 100 fs) of coherently excited photoproducts assigned to $^{3}PtBr_{5}^{-}$ and $^{3}OsBr_{5}^{-}$. This is explained by the fact that one of the lowest triplet excited states in both $PtBr_{6}^{2-}$ and $OsBr_{6}^{2-}$ is repulsive. Surprisingly, the damping time and amplitude of the observed coherent oscillations in the pentabromoosmate (209 cm$^{-1}$) and pentabromoplatinate (112 cm$^{-1}$) species is quite different. The shorter damping time (0.4 ps) of $^{3}PtBr_{5}^{-}$ in comparison with the damping time (1 ps) of $^{3}OsBr_{5}^{-}$ in aqueous solution is related to faster dephasing in $^{3}PtBr_{5}^{-}$. The large-amplitude bending oscillations in pentabromoplatinate are tentatively assigned to the passage of the wavepacket through the Janh-Teller conical intersection(s), whereas in pentabromoosmate, the umbrella type of oscillations appears to be due to the coupling to the Os-Br symmetric stretching mode in the parent dianion. The coherent oscillations in both photoproducts show no dependence on solvent. The results are supported by DFT, TD-DFT and CASSCF/CASPT2 calculations of electronic structures, vertical electronic transitions and harmonic frequencies of initial dianions and photoproducts.en_US
dc.language.isoenen_US
dc.publisherOhio State Universityen_US
dc.titleULTRAFAST EXCITED-STATE DYNAMICS IN MODEL HEXABROMOPLATINATE (IV) AND HEXABROMOOSMIATE (IV) DIANIONS IN THE CONDENSED PHASEen_US
dc.typeArticleen_US
dc.typeImageen_US
dc.typePresentationen_US


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