Coherent Motion Reveals Non‐Ergodic Nature of Internal Conversion between Excited States

Publication: Research - peer-reviewJournal article – Annual report year: 2012

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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 S2→S1 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 S2 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.
Original languageEnglish
JournalChemPhysChem
Publication date2012
Volume13
Issue3
Pages820-827
ISSN1439-4235
DOIs
StatePublished
CitationsWeb of Science® Times Cited: 7
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