Theoretical study of the triplet excited state of PtPOP and the exciplexes M-PtPOP (M = Tl, Ag) in solution and comparison with ultrafast X-ray scattering results

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The [Pt2(H2P2O5)4]4− ions in the ground and excited states and the excited-state complexes M-[Pt2(H2P2O5)4]3− and M2-[Pt2(H2P2O5)4]2− (M = Ag, Tl) were studied in solution with various density functional theory (DFT) functionals from Gaussian 09 and Amsterdam Density Functional (ADF) programs. Calculated results were compared with ultrafast X-ray solution scattering data. Time dependent DFT (TD-DFT) calculations with the B3PW91 functional and unrestricted open shell calculations with the mPBE functional produce good agreement with the experimental results. Compared to gas phase calculations, the surrounding solvent is found to play an important role to shorten the Pt–Pt and M–Pt (M = Ag, Tl) bond lengths, lowering the molecular orbital energies and influences the molecular orbital transitions upon excitation, which stabilizes the excited transient molecules in solution.
Original languageEnglish
JournalChemical Physics
Issue number1
Pages (from-to)117-122
Publication statusPublished - 2012
CitationsWeb of Science® Times Cited: No match on DOI

    Research areas

  • M-[Pt2(H2P2O5)4]3−, Excited state, TD-DFT, [Pt2(H2P2O5)4]4−, M2-[Pt2(H2P2O5)4]2−, Exciplexes

ID: 6434244