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Femtosecond Real-Time Probing of Reactions. 20. Dynamics of Twisting, Alignment, and IVR in thetrans-Stilbene Isomerization Reaction

Baskin, J. S. and Bañares, L. and Pedersen, S. and Zewail, A. H. (1996) Femtosecond Real-Time Probing of Reactions. 20. Dynamics of Twisting, Alignment, and IVR in thetrans-Stilbene Isomerization Reaction. Journal of Physical Chemistry, 100 (29). pp. 11920-11933. ISSN 0022-3654 . http://resolver.caltech.edu/CaltechAUTHORS:20160824-143938158

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Abstract

The femtosecond real-time dynamics of the isomerization reaction of trans-stilbene under collisionless conditions are studied using (2+1) resonance-enhanced multiphoton ionization (REMPI) and femtosecond depletion spectroscopy (FDS) in a pump−probe scheme. The observed transients reflect the macroscopic sample anisotropy decay (rotational coherence) and intramolecular vibrational energy redistribution (IVR) as well as the ethylenic twisting isomerization reaction. Polarization-resolved measurements are performed to isolate the influence of rotational dynamics, and the measured anisotropy decay is compared with theoretical calculations of rotational coherence at room temperature. The IVR and nonradiative (isomerization) processes of trans-stilbene are studied as a function of S_1 excess vibrational energy up to ∼6500 cm^(-1). These results are compared with previous measurements of trans-stilbene under collisionless conditions and with predictions of RRK and RRKM theories.


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http://dx.doi.org/10.1021/jp960909xDOIArticle
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Additional Information:© 1996 American Chemical Society. Received: March 26, 1996. Publication Date (Web): July 18, 1996. Robin Hochstrasser has made many important contributions to chemical physics. One area in which he has played a central role is the study of isomerization. We are delighted to make this contribution, appropriate in subject matter, in honor of this event in The Journal of Physical Chemistry. This research is supported by the National Science Foundation. The authors wish to thank Mr. Obadiah Manley for assistance with the RRKM calculations.
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Record Number:CaltechAUTHORS:20160824-143938158
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20160824-143938158
Official Citation:Femtosecond Real-Time Probing of Reactions. 20. Dynamics of Twisting, Alignment, and IVR in the trans-Stilbene Isomerization Reaction J. S. Baskin, L. Bañares, S. Pedersen, and A. H. Zewail The Journal of Physical Chemistry 1996 100 (29), 11920-11933 DOI: 10.1021/jp960909x
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ID Code:69912
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:26 Aug 2016 17:09
Last Modified:26 Aug 2016 17:09

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