Substituent effects on dynamics at conical intersections : Cyclopentadienes

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DOIResolve DOI: http://doi.org/10.1021/jp911286s
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TypeArticle
Journal titleThe Journal of Physical Chemistry A
Volume114
Issue12
Pages40584064; # of pages: 7
AbstractSubstituent effects on dynamics at conical intersections are investigated by means of femtosecond timeresolved photoelectron spectroscopy for cyclopentadiene and its substituted analogues 1,2,3,4-tetramethylcyclopentadiene, 1,2,3,4,5-pentamethylcyclopentadiene, and 1,2,3,4-tetramethyl-5-propylcyclopentadiene. By UV excitation to the S2 (11B2) state, the influence of these substitutions on dynamics for the initially excited S2 (11B2) surface and the spectroscopically dark S1 (21A1) surface were investigated. We observed that the dynamics depend only on a small number of specific vibrations. Whereas dynamics at the S2/S1-conical intersection are independent of substitution at the 5-position, internal conversion dynamics on the S1 (21A1) surface slow down as the inertia of the 5-substituent increases. Contrary to the expectations of simple models of radiationless transitions, an increasing density of states does not lead to faster processes, suggesting that a true dynamical picture of vibrational motions at conical intersections will be required.
Publication date
LanguageEnglish
AffiliationNRC Steacie Institute for Molecular Sciences; National Research Council Canada
Peer reviewedYes
NPARC number17673460
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Record identifierabe61567-bc3d-4da8-8fbb-4d11f64ccc91
Record created2011-04-01
Record modified2017-03-23
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