Competing ultrafast intersystem crossing and internal conversion in the "channel 3" region of benzene

We report new, detailed, femtosecond time-resolved photoelectron spectroscopy experiments and calculations investigating the competition between ultrafast internal conversion and ultrafast intersystem crossing in electronically and vibrationally excited benzene at the onset of "channel 3"....

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Veröffentlicht in:Physical chemistry chemical physics : PCCP 2010-01, Vol.12 (48), p.1567-15615
Hauptverfasser: Minns, R. S, Parker, D. S. N, Penfold, T. J, Worth, G. A, Fielding, H. H
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container_end_page 15615
container_issue 48
container_start_page 1567
container_title Physical chemistry chemical physics : PCCP
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creator Minns, R. S
Parker, D. S. N
Penfold, T. J
Worth, G. A
Fielding, H. H
description We report new, detailed, femtosecond time-resolved photoelectron spectroscopy experiments and calculations investigating the competition between ultrafast internal conversion and ultrafast intersystem crossing in electronically and vibrationally excited benzene at the onset of "channel 3". Using different probe energies to record the total photoelectron yield as a function of pump-probe delay we are able to confirm that S 1 , T 1 and T 2 electronic states are involved in the excited state dynamics. Time-resolved photoelectron spectroscopy measurements then allow us to unravel the evolution of the S 1 , T 1 and T 2 components of the excited state population and, together with complementary quantum chemistry and quantum dynamics calculations, support our earlier proposal that ultrafast intersystem crossing competes with internal conversion ( Chem. Phys. Lett. , 2009, 469 , 43). Time-resolved photoelectron spectroscopy experiments and quantum dynamics calculations reveal an ultrafast intersystem crossing in the "channel 3" region of benzene.
doi_str_mv 10.1039/c001671c
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Time-resolved photoelectron spectroscopy measurements then allow us to unravel the evolution of the S 1 , T 1 and T 2 components of the excited state population and, together with complementary quantum chemistry and quantum dynamics calculations, support our earlier proposal that ultrafast intersystem crossing competes with internal conversion ( Chem. Phys. Lett. , 2009, 469 , 43). 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source Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection
subjects Benzene
Channels
Dynamics
Excitation spectra
Internal conversion
Mathematical analysis
Photoelectron spectroscopy
Quantum chemistry
title Competing ultrafast intersystem crossing and internal conversion in the "channel 3" region of benzene
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