Journal article
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
Synchrotron Soleil1
University of Copenhagen2
Metal Structures in Four Dimensions, Materials Research Division, Risø National Laboratory for Sustainable Energy, Technical University of Denmark3
Materials Research Division, Risø National Laboratory for Sustainable Energy, Technical University of Denmark4
Risø National Laboratory for Sustainable Energy, Technical University of Denmark5
Nano-Microstructures in Materials, Materials Research Division, Risø National Laboratory for Sustainable Energy, Technical University of Denmark6
European Synchrotron Radiation Facility7
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.
Language: | English |
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Year: | 2012 |
Pages: | 117-122 |
ISSN: | 18734421 and 03010104 |
Types: | Journal article |
DOI: | 10.1016/j.chemphys.2011.11.034 |
ORCIDs: | Haldrup, Martin Kristoffer , Nielsen, Martin Meedom and 0000-0003-4812-0522 |