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  Real-time observation of intra- and intermolecular vibrational energy flow of selectively excited alkyl iodides in solution: The effect of chemical substitution

Assmann, J., Charvat, A., Schwarzer, D., Kappel, C., Luther, K., & Abel, B. (2002). Real-time observation of intra- and intermolecular vibrational energy flow of selectively excited alkyl iodides in solution: The effect of chemical substitution. Journal of Physical Chemistry A, 106(21), 5197-5201. Retrieved from http://pubs.acs.org/doi/pdfplus/10.1021/jp015552y.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0012-F3BB-C Version Permalink: http://hdl.handle.net/11858/00-001M-0000-002A-3954-5
Genre: Journal Article

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 Creators:
Assmann, J.1, Author              
Charvat, A.1, Author              
Schwarzer, D.2, Author              
Kappel, C., Author
Luther, K.1, Author              
Abel, B.3, Author
Affiliations:
1Department of Spectroscopy and Photochemical Kinetics, MPI for biophysical chemistry, Max Planck Society, ou_578624              
2Research Group of Reaction Dynamics, MPI for biophysical chemistry, Max Planck Society, ou_578601              
3Max Planck Society, ou_persistent13              

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 Abstract: Intramolecular vibrational energy redistribution (IVR) and intermolecular vibrational energy transfer (VET) of two alkyl iodides (CF3CH2I and CH3CH2-I) selectively excited in the two quanta overtone region of the CH stretch vibration (upsilon(CH) = 2) were measured in real time in solution. In this study, we have focused on the effect of chemical substitution on the mechanisms and time scales of IVR and VET of this family of molecules. With a simple model. we have obtained global IVR and VET rate coefficients for both molecules. The magnitude and the variation of the relaxation rates upon chemical substitution provide evidence for a survival of hierarchical IVR in these solvated molecules. which is governed by specific low-order intramolecular interactions and which can be rationalized with a simple low-order coupling model. At the same time, the general assumption that VET is simply dominated by the lowest- frequency modes in a molecule is not supported.

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Language(s): eng - English
 Dates: 2002-05-30
 Publication Status: Published in print
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 Rev. Method: Peer
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Title: Journal of Physical Chemistry A
Source Genre: Journal
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Pages: - Volume / Issue: 106 (21) Sequence Number: - Start / End Page: 5197 - 5201 Identifier: -