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A multipronged comparative study of the ultraviolet photochemistry of 2-, 3-, and 4-chlorophenol in the gas phase
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Harris, S. J., Karsili, T. N. V., Murdock, D., Oliver, T. A. A., Wenge, A. M., Zaouris, D. K., Ashfold, M. N. R., Harvey, J. N., Few, J. D., Gowrie, S., Hancock, G., Hadden, David J., Roberts, Gareth M., Stavros, Vasilios G., Spighi, G., Poisson, L. and Soep, B. (2015) A multipronged comparative study of the ultraviolet photochemistry of 2-, 3-, and 4-chlorophenol in the gas phase. Journal of Physical Chemistry A, 119 (23). pp. 6045-6056. doi:10.1021/jp511879k ISSN 1089-5639.
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Official URL: http://dx.doi.org/10.1021/jp511879k
Abstract
The S1(1ππ*) state of the (dominant) syn-conformer of 2-chlorophenol (2-ClPhOH) in the gas phase has a subpicosecond lifetime, whereas the corresponding S1 states of 3- and 4-ClPhOH have lifetimes that are, respectively, ∼2 and ∼3-orders of magnitude longer. A range of experimental techniques–electronic spectroscopy, ultrafast time-resolved photoion and photoelectron spectroscopies, H Rydberg atom photofragment translational spectroscopy, velocity map imaging, and time-resolved Fourier transform infrared emission spectroscopy–as well as electronic structure calculations (of key regions of the multidimensional ground (S0) state potential energy surface (PES) and selected cuts through the first few excited singlet PESs) have been used in the quest to explain these striking differences in excited state lifetime. The intramolecular O–H···Cl hydrogen bond specific to syn-2-ClPhOH is key. It encourages partial charge transfer and preferential stabilization of the diabatic 1πσ* potential (relative to that of the 1ππ* state) upon stretching the C–Cl bond, with the result that initial C–Cl bond extension on the adiabatic S1 PES offers an essentially barrierless internal conversion pathway via regions of conical intersection with the S0 PES. Intramolecular hydrogen bonding is thus seen to facilitate the type of heterolytic dissociation more typically encountered in solution studies.
Item Type: | Journal Article | ||||
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||
Journal or Publication Title: | Journal of Physical Chemistry A | ||||
Publisher: | American Chemical Society | ||||
ISSN: | 1089-5639 | ||||
Official Date: | 6 February 2015 | ||||
Dates: |
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Volume: | 119 | ||||
Number: | 23 | ||||
Page Range: | pp. 6045-6056 | ||||
DOI: | 10.1021/jp511879k | ||||
Status: | Peer Reviewed | ||||
Publication Status: | Published | ||||
Access rights to Published version: | Restricted or Subscription Access |
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