The Role of πσ* Excited States in the Photodissociation of Heteroaromatic Molecules

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Science  16 Jun 2006:
Vol. 312, Issue 5780, pp. 1637-1640
DOI: 10.1126/science.1125436

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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 1πσ* 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.

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