Vibrational state distribution and relaxation of vinoxy radicals

Autor:	Hongmei Su, Richard Bersohn
Rok vydání:	2001
Předmět:	chemistry.chemical_classification Radical Relaxation (NMR) Photodissociation General Physics and Astronomy Vinyl ether Photochemistry Spectral line Propene chemistry.chemical_compound chemistry Excited state medicine Physical and Theoretical Chemistry Alkyl medicine.drug
Zdroj:	The Journal of Chemical Physics. 115:217-224
ISSN:	1089-7690 0021-9606
DOI:	10.1063/1.1369602
Popis:	The vinoxy radical ⋅CH2CHO is a product of the reaction of O(3P) atoms with terminal alkenes and can also be made by photodissociation of an alkyl vinyl ether. In either case it is formed in a vibrationally excited state. The nascent radical displays a rich electronic spectrum to the red of its X→B band origin consisting of bands originating from vibrationally excited states. Some transitions, true “hot bands,” terminate on the vibrationless B state; others, sequence bands, terminate on vibrationally excited B states. The spectra become unobservably weak at a certain energy. The difference between that energy and the energy of the band origin is roughly the maximum vibrational energy in the radical. This is 5600 cm−1 for the vinoxy produced by photodissociation of ethyl vinyl ether at 193 nm and 3200 cm−1 for the product of the reaction of O(3P) with ethylene, propene, 1-butene, and 1-pentene. There is a remarkable cooling of the vibrations as the hydrocarbon chain lengthens. The average vibrational energ...
Databáze:	OpenAIRE
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