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

TY - JOUR

T1 - 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

AU - Kong, Qingyu

AU - Kjær, Kasper S.

AU - Haldrup, Kristoffer

AU - Sauer, Stephan P. A.

AU - Brandt van Driel, Tim

AU - Christensen, Morten

AU - Nielsen, Martin Meedom

AU - Wulff, Michael

PY - 2012/1/17

Y1 - 2012/1/17

N2 - The [Pt 2(H 2P 2O 5) 4] 4- ions in the ground and excited states and the excited-state complexes M-[Pt 2(H 2P 2O 5) 4] 3- and M 2-[Pt 2(H 2P 2O 5) 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.

AB - The [Pt 2(H 2P 2O 5) 4] 4- ions in the ground and excited states and the excited-state complexes M-[Pt 2(H 2P 2O 5) 4] 3- and M 2-[Pt 2(H 2P 2O 5) 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.

U2 - 10.1016/j.chemphys.2011.11.034

DO - 10.1016/j.chemphys.2011.11.034

M3 - Journal article

SN - 0301-0104

VL - 393

SP - 117

EP - 122

JO - Chemical Physics

JF - Chemical Physics

IS - 1

ER -