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Exploring the time-scales of H-atom detachment from photoexcited phenol-h(6) and phenol-d(5): statistical vs nonstatistical decay
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Iqbal, Azhar, Cheung, Michelle, Nix, Michael G. D. and Stavros, Vasilios G. (2009) Exploring the time-scales of H-atom detachment from photoexcited phenol-h(6) and phenol-d(5): statistical vs nonstatistical decay. Journal of Physical Chemistry A, Vol.113 (No.29). pp. 8157-8163. doi:10.1021/jp9031223
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Official URL: http://dx.doi.org/10.1021/jp9031223
Abstract
The prevalence of 1 pi sigma* states in the photochemistry of heteroaromatics is becoming increasingly clear from the recent literature. Photodissociation measurements have shown that following excitation of phenol molecules above the S-1/S-2 conical intersection, H-atoms are eliminated with two distinct ranges of kinetic energy release. Those with high kinetic energy are attributed to direct dissociation while those with low kinetic energy are traditionally attributed to indirect dissociation or statistical unimolecular decay, both pathways giving electronic ground-state phenoxyl fragments. Using a combination of femtosecond pump/probe spectroscopy and velocity map ion imaging techniques, the time and energy resolved H-atom elimination in phenol-h(6) and phenol-d(5), following excitation at 200 nm has been measured. At the lowest kinetic energies, the H-atom elimination from phenol-d(5) occurs in < 150 fs, in sharp contrast to what one expects from a statistical decay process. This implies that these H-atoms are formed through a direct dissociation process yielding electronically excited phenoxyl fragments.
| Item Type: | Journal Article | ||||
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| Subjects: | Q Science > QD Chemistry Q Science > QP Physiology |
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| Divisions: | Faculty of Science > Chemistry | ||||
| Library of Congress Subject Headings (LCSH): | Photodissociation, Molecular dynamics, Tryptophan, Photochemistry, Pyrroles, Elimination reactions | ||||
| Journal or Publication Title: | Journal of Physical Chemistry A | ||||
| Publisher: | American Chemical Society | ||||
| ISSN: | 1089-5639 | ||||
| Official Date: | 23 July 2009 | ||||
| Dates: |
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| Volume: | Vol.113 | ||||
| Number: | No.29 | ||||
| Number of Pages: | 7 | ||||
| Page Range: | pp. 8157-8163 | ||||
| DOI: | 10.1021/jp9031223 | ||||
| Status: | Peer Reviewed | ||||
| Publication Status: | Published | ||||
| Access rights to Published version: | Restricted or Subscription Access | ||||
| Funder: | Royal Society (Great Britain), Engineering and Physical Sciences Research Council (EPSRC), University of Warwick | ||||
| Grant number: | EP/E0 11187 (EPSRC) |
Data sourced from Thomson Reuters' Web of Knowledge
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