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Coherent Motion Reveals Non‐Ergodic Nature of Internal Conversion between Excited States
Author(s) -
Kuhlman Thomas S.,
Sølling Theis I.,
Møller Klaus B.
Publication year - 2012
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201100929
Subject(s) - chemistry , excited state , internal conversion , cyclopentanone , spectroscopy , molecule , atomic physics , molecular physics , physics , quantum mechanics , spectral line , biochemistry , organic chemistry , catalysis
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.