Unusual vibrational predissociation dynamics of aromatic clusters with internal rotation

Charles S. Parmenter; ZhongQuan Zhao

doi:10.1117/12.220845

18 September 1995 Unusual vibrational predissociation dynamics of aromatic clusters with internal rotation

Charles S. Parmenter, ZhongQuan Zhao

Proceedings Volume 2548, Laser Techniques for State-Selected and State-to-State Chemistry III; (1995) https://doi.org/10.1117/12.220845
Event: SPIE's 1995 International Symposium on Optical Science, Engineering, and Instrumentation, 1995, San Diego, CA, United States

Abstract

A broad picture is emerging of the role played by methyl internal rotation on intramolecular vibrational redistribution (IVR) among ring modes of the benzene ring and on IVR between the ring modes and the van der Waals modes of complexes. The studies are based on the benchmark system p-difluorobenzene (pDFB) for which IVR at 300 K from many excited electronic state initial levels has been characterized long ago by oxygen quenching (chemical timing) of fluorescence. Replacement of a fluorine with a methyl group to make p- fluorotoluene (pFT) provides the methyl internal rotation that has strong interaction with the ring. A view of the methyl rotor effect on vibrational predissociation (VP) is obtained by studies of van der Waals complexes between these aromatics and Ar. The VP characteristics are qualitatively changed when a methyl internal rotation is introduced onto the ring. VP from lower initial levels of the pFT complex loses the high vibrational channel selectivity that is the signature of all other aromatic complexes. Those changes are traced back to an IVR process involving both ring modes and van der Waals modes that precedes the dissociation.

Citation Download Citation

Charles S. Parmenter and ZhongQuan Zhao "Unusual vibrational predissociation dynamics of aromatic clusters with internal rotation", Proc. SPIE 2548, Laser Techniques for State-Selected and State-to-State Chemistry III, (18 September 1995); https://doi.org/10.1117/12.220845

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