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Science 16 June 2006:
Vol. 312. no. 5780, pp. 1637 - 1640
DOI: 10.1126/science.1125436
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Reports

The Role of {pi}{sigma}* Excited States in the Photodissociation of Heteroaromatic Molecules

M. N. R. Ashfold,* B. Cronin, A. L. Devine, R. N. Dixon, M. G. D. Nix

High-resolution measurements of the kinetic energies of hydrogen atom fragments formed during ultraviolet photolysis of imidazole, pyrrole, and phenol in the gas phase confirm that N(O)–H bond fission is an important nonradiative decay process from their respective 1{pi}{sigma}* excited states. The measurements also reveal that the respective cofragments (imidazolyl, pyrrolyl, and phenoxyl) are formed in very limited subsets of their available vibrational states. Identification of these product states yields uniquely detailed insights into the vibronic couplings involved in the photoinduced evolution from parent molecule to ultimate fragments.

School of Chemistry, University of Bristol, Bristol, BS8 1TS UK.

* To whom correspondence should be addressed. E-mail: mike.ashfold{at}bris.ac.uk

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THIS ARTICLE HAS BEEN CITED BY OTHER ARTICLES:
Chemical Dynamics Special Feature: Exploring nuclear motion through conical intersections in the UV photodissociation of phenols and thiophenol.
M. N. R. Ashfold, A. L. Devine, R. N. Dixon, G. A. King, M. G .D. Nix, and T. A. A. Oliver (2008)
PNAS 105, 12701-12706
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