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Direct observation of a mode-selective (non-RRKM) van der Waals reaction by picosecond photofragment spectroscopy

Semmes, David H. and Baskin, J. Spencer and Zewail, Ahmed H. (1987) Direct observation of a mode-selective (non-RRKM) van der Waals reaction by picosecond photofragment spectroscopy. Journal of the American Chemical Society, 109 (13). pp. 4104-4106. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20160908-154009851

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Abstract

The idea of directing reactions by selectively exciting particular vibrational modes with lasers (laser-selective chemistry) has stimulated much experimental and theoretical research aimed at exploring its feasibility and the deviation from statistical RRKM behavior in large molecules. In the absence of collisions, the yield and rate of a reaction will be determined by the specific rate of intramolecular vibrational-energy redistribution (IVR) from the initial mode excited to the other modes in the molecule and by the rate of bond breaking (vibrational predissociation). If k_(lvR) is larger than k_(VP), then the chemistry is from a statistically formed distribution of vibrational states and a statistical behavior (RRKM) may prevail, even if a laser is used to selectively excite the initial state of the reagent. It is this interplay between IVR and VP that determines the mode selectivity of the reaction. Excitation of the molecule with short enough pulses, short compared to k_(lVR)^(-l) and k_(vP)^(-l), should allow us to view these processes in real time and hopefully establish conditions for nonstatistical behavior.


Item Type:Article
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URLURL TypeDescription
http://dx.doi.org/10.1021/ja00247a041DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja00247a041PublisherArticle
Additional Information:© 1987 American Chemical Society. Received February 17, 1987. This work supported by a grant from the National Science Foundation. Some support was also provided by the President's Fund.
Funders:
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NSFUNSPECIFIED
Caltech President’s FundUNSPECIFIED
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Other Numbering System NameOther Numbering System ID
Arthur Amos Noyes Laboratory of Chemical Physics7555
Issue or Number:13
Record Number:CaltechAUTHORS:20160908-154009851
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160908-154009851
Official Citation:Direct observation of a mode-selective (non-RRKM) van der Waals reaction by picosecond photofragment spectroscopy David H. Semmes, J. Spencer Baskin, and Ahmed H. Zewail Journal of the American Chemical Society 1987 109 (13), 4104-4106 DOI: 10.1021/ja00247a041
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:70217
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:13 Sep 2016 23:28
Last Modified:03 Oct 2019 10:29

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