Skip to main content

Research Repository

See what's under the surface

Advanced Search

Probing the origins of vibrational mode specificity in intramolecular dynamics through picosecond time-resolved photoelectron imaging studies

Davies, Julia A.; Whalley, Laura; Reid, Katharine L.

Authors

Julia A. Davies

Laura Whalley

Katharine L. Reid



Abstract

We have studied the intramolecular dynamics induced by selective photoexcitation of two near-isoenergetic vibrational states in S1 p-fluorotoluene using picosecond time-resolved photoelectron imaging. We find that similar dynamics ensue following the preparation of the 13111 and 7a111 states that lie at 1990 cm-1 and 2026 cm-1, and that these dynamics are mediated by a single strongly coupled doorway state in each case. However, the lifetimes differ by a factor of three, suggesting an influence of the vibrational character of the modes involved. Our results clearly show the contribution of torsion-vibration coupling to the dynamics; this is further corroborated by comparison with the 7a111 state in S1 p-difluorobenzene, which lies at 2068 cm-1. We invoke a model in which van der Waals interactions between methyl hydrogen atoms and nearby ring carbon and hydrogen atoms leads to mixing of the vibrational and torsional states. This model predicts that enhanced torsion-vibration coupling occurs when mode 7a is excited, consistent with our observations.

Journal Article Type Article
Publication Date Feb 7, 2017
Journal Physical Chemistry Chemical Physics
Print ISSN 1463-9076
Electronic ISSN 1463-9084
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 19
Issue 7
Pages 5051-5062
APA6 Citation Davies, J. A., Whalley, L., & Reid, K. L. (2017). Probing the origins of vibrational mode specificity in intramolecular dynamics through picosecond time-resolved photoelectron imaging studies. Physical Chemistry Chemical Physics, 19(7), 5051-5062 . doi:10.1039/c6cp08132k
DOI https://doi.org/10.1039/c6cp08132k
Publisher URL https://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C6CP08132K#!divAbstract
Copyright Statement Copyright information regarding this work can be found at the following address: http://eprints.nottingh.../end_user_agreement.pdf
Additional Information

Composition Type:

Files

Davies 2016 revised (002).pdf (1.4 Mb)
PDF

Copyright Statement
Copyright information regarding this work can be found at the following address: http://eprints.nottingham.ac.uk/end_user_agreement.pdf





Downloadable Citations

;