Real-time detection of doorway states in the intramolecular vibrational energy redistribution of the OH/OD stretch vibration of phenol

Journal of Chemical Physics Volume 121 Issue 23 Page 11530-11534 published_at 2004-12-15
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Title ( eng )
Real-time detection of doorway states in the intramolecular vibrational energy redistribution of the OH/OD stretch vibration of phenol
Creator
Yamada Yuji
Mikami Naohiko
Source Title
Journal of Chemical Physics
Volume 121
Issue 23
Start Page 11530
End Page 11534
Abstract
A picosecond time-resolved IR-UV pump-probe spectroscopic study was carried out for the intramolecular vibrational energy redistribution of the OH/OD stretching vibration of isolated phenol and its isotopomers in supersonic beams. The time evolution due to IVR showed a significant isotope effect; the OH stretch vibration showed a single exponential decay and its lifetime is greatly lengthened upon the deuterium substitution of the CH group. The OD stretch vibration exhibited prominent quantum beats. Especially, in phenol-d1 (C6H5OD), the electronic transitions from the doorway states were clearly observed. They exhibited an out-of-phase quantum beat with respect to that of the OD stretch level and disappeared due to further IVR to the dense bath states. The transient spectra as well as the time evolution clearly evidenced the tier-model of the description of intramolecular vibrational energy redistribution.
Language
eng
Resource Type journal article
Publisher
American Institute of Physics
Date of Issued 2004-12-15
Rights
Copyright (c) 2004 American Institute of Physics.
Publish Type Version of Record
Access Rights open access
Source Identifier
[ISSN] 0021-9606
[DOI] 10.1063/1.1829634
[NCID] AA00694991
[DOI] http://dx.doi.org/10.1063/1.1829634