Nov, 2008
Ultrafast bimolecular radical reaction between S1 p-terphenyl and carbon tetrachloride: mode-specific acceleration of vibrational dephasing in reactant molecule
JOURNAL OF RAMAN SPECTROSCOPY
- Volume
- 39
- Number
- 11
- First page
- 1512
- Last page
- 1517
- Language
- English
- Publishing type
- Research paper (scientific journal)
- DOI
- 10.1002/jrs.2104
- Publisher
- JOHN WILEY & SONS LTD
Ultrafast bimolecular radical reaction proceeds between photoexcited p-terphenyl and carbon tetrachloride. The lifetime of the first excited singlet (Si) state of p-terphenyl in carbon tetrachloride measured with picosecond time-resolved fluorescence spectroscopy is 5.6 ps, shorter than the typical lifetime in ordinary solvents, 0.95-2.8 ns, by a factor of 170 or more. Time-resolved infrared spectroscopy reveals the generation of the trichloromethyl (CCl(3)) radical as a reaction intermediate. The decay kinetics of the CCl(3) radical indicates that the CCl(3) radical and the p-terphenyl-Cl radical adduct, both of which are produced simultaneously by a radical reaction between S(1) p-terphenyl and carbon tetrachloride, recombine to form the product. The picosecond time-resolved Raman spectrum of the reactant S(1) p-terphenyl shows that the dephasing process for the four vibrational modes at 1640, 1497, 1180, and 1017 cm(-1) is selectively accelerated in carbon tetrachloride. The four vibrational modes probably have a large contribution from the motion of a specific atom or atoms where the intermolecular interaction that induces the bimolecular reaction is present. Copyright (C) 2008 John Wiley & Sons, Ltd.
- Link information
- ID information
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- DOI : 10.1002/jrs.2104
- ISSN : 0377-0486
- Web of Science ID : WOS:000261206200004