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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Coherent Motion Reveals Non‐Ergodic Nature of Internal Conversion between Excited States. / Kuhlman, Thomas Scheby; Sølling, Theis I.; Møller, Klaus Braagaard.

In: ChemPhysChem, Vol. 13, No. 3, 2012, p. 820-827.

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

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Kuhlman, Thomas Scheby; Sølling, Theis I.; Møller, Klaus Braagaard / Coherent Motion Reveals Non‐Ergodic Nature of Internal Conversion between Excited States.

In: ChemPhysChem, Vol. 13, No. 3, 2012, p. 820-827.

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

Bibtex

@article{f011c04f34684cc98063e9d819259fd5,
title = "Coherent Motion Reveals Non‐Ergodic Nature of Internal Conversion between Excited States",
publisher = "Wiley - V C H Verlag GmbH & Co. KGaA",
author = "Kuhlman, {Thomas Scheby} and Sølling, {Theis I.} and Møller, {Klaus Braagaard}",
year = "2012",
doi = "10.1002/cphc.201100929",
volume = "13",
number = "3",
pages = "820--827",
journal = "ChemPhysChem",
issn = "1439-4235",

}

RIS

TY - JOUR

T1 - Coherent Motion Reveals Non‐Ergodic Nature of Internal Conversion between Excited States

A1 - Kuhlman,Thomas Scheby

A1 - Sølling,Theis I.

A1 - Møller,Klaus Braagaard

AU - Kuhlman,Thomas Scheby

AU - Sølling,Theis I.

AU - Møller,Klaus Braagaard

PB - Wiley - V C H Verlag GmbH & Co. KGaA

PY - 2012

Y1 - 2012

N2 - 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.

AB - 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.

U2 - 10.1002/cphc.201100929

DO - 10.1002/cphc.201100929

JO - ChemPhysChem

JF - ChemPhysChem

SN - 1439-4235

IS - 3

VL - 13

SP - 820

EP - 827

ER -