Toluene spectroscopy - JPC A- submitted - revised version.pdf (999.57 kB)
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Electronic spectroscopy of toluene in helium nanodroplets : evidence for a long-lived excited state.

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journal contribution
posted on 23.01.2014, 13:34 by Benjamin Shepperson, Jon Tandy, Adrian Boatwright, Cheng Feng, Daniel Spence, Andrew Shirley, Shengfu Yang, Andrew M. Ellis
Optical excitation of toluene to the S[subscript 1] electronic state in helium nanodroplets is found to alter the rate of production of the fragment ions C[subscript 7]H[subscript 7][superscript +] and C[subscript 5]H[subscript 5][superscript +] when the droplets are subjected to subsequent electron ionization. The optical excitation process reduces the abundance of C[subscript 7]H[subscript 7][superscript +] ions delivered into the gas phase, whereas C[subscript 5]H[subscript 5][superscript +] ions become more abundant beyond a minimum droplet size. This process contrasts with normal optical depletion spectroscopy, where the optical absorption of a molecular dopant in a helium nanodroplet shrinks the helium droplet, and thus, the electron impact cross-sections because of dissipation of the absorbed energy by evaporative loss of helium atoms. The observations here are interpreted in terms of formation of an excited state in the neutral molecule, which survives for several hundred μs. This long-lived excited state, which is assumed to be the lowest triplet electronic state, shows different cross-sections for production of C[subscript 7]H[subscript 7][superscript +] and C[subscript 5]H[subscript 5][superscript +] relative to the S[subscript 0] state.

History

Citation

Journal of Physical Chemistry A, 2013, 117 (50), pp 13591–13595

Author affiliation

/Organisation/COLLEGE OF SCIENCE AND ENGINEERING/Department of Chemistry

Version

AM (Accepted Manuscript)

Published in

Journal of Physical Chemistry A

Publisher

American Chemical Society

issn

1089-5639

eissn

1520-5215

Copyright date

2013

Available date

23/09/2014

Publisher version

http://pubs.acs.org/doi/abs/10.1021/jp407577m

Notes

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry A, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jp407577m

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en

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