Back to Search Start Over

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

Authors :
Qingyu Kong
Kasper S. Kjær
Tim Brandt van Driel
Kristoffer Haldrup
Morten Christensen
Michael Wulff
Stephan P. A. Sauer
Martin Nielsen
Source :
Chemical Physics. 393:117-122
Publication Year :
2012
Publisher :
Elsevier BV, 2012.

Abstract

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

Details

ISSN :
03010104
Volume :
393
Database :
OpenAIRE
Journal :
Chemical Physics
Accession number :
edsair.doi...........2e13ca1659730bb684e4762cae1485a0
Full Text :
https://doi.org/10.1016/j.chemphys.2011.11.034