Role of πσ Excited States in the Photodissociation of Heteroaromatic Molecules

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 measureme...

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Bibliographic Details
Published in:Science (American Association for the Advancement of Science) 2006-06, Vol.312 (5780), p.1637-1640
Main Authors: Ashfold, M.N.R, Cronin, B, Devine, A.L, Dixon, R.N, Nix, M.G.D
Format: Article
Language:English
Subjects:
Atomic and molecular physics
Atoms
Chemical bonding
Diffuse spectra
predissociation, photodissociation
Exact sciences and technology
Ground state
Imidazoles
Molecular properties and interactions with photons
Molecules
Phenols
Photoexcitation
Photolysis
Photon interactions with molecules
Physics
Pyrroles
Vibration
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Summary: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.
ISSN:0036-8075
1095-9203
DOI:10.1126/science.1125436