Propensity towards H photofragments in the photodissociation of CD3NH2 pre-excited to the first N–H stretch overtone

Autor:	Ilana Bar, Ran Marom, Uzi Zecharia, Salman Rosenwaks
Rok vydání:	2008
Předmět:	Chemistry Overtone Photodissociation Biophysics Condensed Matter Physics Photochemistry Transition state Deuterium Excited state Picosecond Ionization Physical and Theoretical Chemistry Molecular Biology Excitation
Zdroj:	Molecular Physics. 106:213-222
ISSN:	1362-3028 0026-8976
Popis:	Vibrationally mediated photodissociation combined with (2 + 1) resonantly enhanced multiphoton ionization detection of H and D photoproducts was used to assess selective bond fission in partially deuterated methylamine, CD3NH2. Jet-cooled action spectra and Doppler profiles of the H and D photofragments were obtained via ∼243.1 nm photodissociation of the parent containing two quanta of N–H stretch excitation. The multiband action spectra indicate that the energy flow out of the initially prepared N–H stretch to the bath states is on a picosecond time scale and that the 2v 10 state (antisymmetric N–H stretch) is longer lived than the other states. Although the specificity attained by N–H stretch excitation was lost, the photofragment yield of H was nine times higher than that of D, indicating preferential N–H bond fission due to lower transition states on the excited state surface.
Databáze:	OpenAIRE
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