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Picosecond photofragment spectroscopy. III. Vibrational predissociation of van der Waals’ clusters

Knee, Joseph L. and Khundkar, Lutfur R. and Zewail, Ahmed H. (1987) Picosecond photofragment spectroscopy. III. Vibrational predissociation of van der Waals’ clusters. Journal of Chemical Physics, 87 (1). pp. 115-127. ISSN 0021-9606. https://resolver.caltech.edu/CaltechAUTHORS:20160906-090612288

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Abstract

This paper, last in this series, reports on the picosecond dynamics of vibrational predissociation in beam‐cooled van der Waals’ clusters. Reaction rates have been measured for clusters (1:1) of phenol and cresol (p‐methylphenol) with benzene by the picosecond pump–probe photoionization mass‐spectrometry technique. Dissociation to form phenol (cresol) and benzene takes place from vibrational levels of the S_1 state of phenol (cresol) prepared by the pump laser. The predissociation rates were measured for a number of different excess energies upto ∼2500 cm^(−1), and the reaction threshold was found to be 1400 cm^(−1) above the S_1 origin for phenol–benzene and ∼1795 cm^(−1) for cresol–benzene, respectively. For phenol–benzene, the predissociation rates, following excitation of ring‐type modes, vs excess energy vary more or less smoothly. Cresol–benzene exhibits biexponential decay, with the fast component becoming more dominant at higher energies. A non‐RRKM model involving division of the vibrational phase space is discussed to explain this observation.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.453608DOIArticle
http://scitation.aip.org/content/aip/journal/jcp/87/1/10.1063/1.453608PublisherArticle
Additional Information:© 1987 American Institute of Physics. Received 09 December 1986 Accepted 11 February 1987. This work was supported by a grant from the National Science Foundation (DMR 85-21191).
Funders:
Funding AgencyGrant Number
NSFDMR 85-21191
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Arthur Amos Noyes Laboratory of Chemical Physics7515
Issue or Number:1
Record Number:CaltechAUTHORS:20160906-090612288
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160906-090612288
Official Citation:Picosecond photofragment spectroscopy. III. Vibrational predissociation of van der Waals’ clusters Knee, Joseph L. and Khundkar, Lutfur R. and Zewail, Ahmed H., The Journal of Chemical Physics, 87, 115-127 (1987), DOI:http://dx.doi.org/10.1063/1.453608
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:70169
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:09 Sep 2016 18:35
Last Modified:03 Oct 2019 10:28

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