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. doi:10.1021/ja00247a041. 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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| 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. | |||||||||
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| Issue or Number: | 13 | |||||||||
| DOI: | 10.1021/ja00247a041 | |||||||||
| 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: | 11 Nov 2021 04:26 |
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