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

Yuji Yamada | Zendy; Naohiko Mikami | Zendy; Takayuki Ebata | Zendy

Open Access

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

Author(s) -

Yuji Yamada,

Naohiko Mikami,

Takayuki Ebata

Publication year - 2004

Publication title -

the journal of chemical physics

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.071

H-Index - 357

eISSN - 1089-7690

pISSN - 0021-9606

DOI - 10.1063/1.1829634

Subject(s) - intramolecular force , chemistry , redistribution (election) , quantum beats , picosecond , kinetic isotope effect , deuterium , vibration , isotopomers , atomic physics , fermi resonance , photochemistry , molecular physics , infrared spectroscopy , stereochemistry , laser , physics , optics , molecule , organic chemistry , quantum mechanics , politics , political science , law , excited state

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.

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