Document Detail


Coherent Motion Reveals Non-Ergodic Nature of Internal Conversion between Excited States.
MedLine Citation:
PMID:  22279007     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
We found that specific nuclear motion along low-frequency modes is effective in coupling electronic states and that this motion prevail in some small molecules. Thus, in direct contradiction to what is expected based on the standard models, the internal conversion process can proceed faster for smaller molecules. Specifically, we focus on the S(2) →S(1) internal conversion in cyclobutanone, cyclopentanone, and cyclohexanone. By means of time-resolved mass spectrometry and photoelectron spectroscopy the relative rate of this transition is determined to be 13:2:1. Remarkably, we observe coherent nuclear motion on the S(2) surface in a ring-puckering mode and motion along this mode in combination with symmetry considerations allow for a consistent explanation of the observed relative time-scales not afforded by only considering the density of vibrational states or other aspects of the standard models.
Authors:
Thomas S Kuhlman; Theis I Sølling; Klaus B Møller
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-1-25
Journal Detail:
Title:  Chemphyschem : a European journal of chemical physics and physical chemistry     Volume:  -     ISSN:  1439-7641     ISO Abbreviation:  -     Publication Date:  2012 Jan 
Date Detail:
Created Date:  2012-1-26     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  100954211     Medline TA:  Chemphyschem     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Copyright Information:
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Affiliation:
Department of Chemistry, Technical University of Denmark, Kemitorvet 207, DK-2800 Kgs. Lyngby (Denmark).
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