Intersystem Crossing and Nonadiabatic Product Channels in the Photodissociation of N2O4 at 193 nm

Autor:	Jonathan P. D. Abbatt, Stephen L. Curry, Laurie J. Butler, Melita L. Morton, Julie A. Mueller
Rok vydání:	2000
Předmět:	Fission products Intersystem crossing Fission Ab initio quantum chemistry methods Chemistry Excited state Photodissociation Physical and Theoretical Chemistry Configuration interaction Atomic physics Dissociation (chemistry)
Zdroj:	The Journal of Physical Chemistry A. 104:4825-4832
ISSN:	1520-5215 1089-5639
Popis:	This paper presents velocity and angular distribution measurements of the products of N2O4 photodissociated at 193 nm. The data show evidence for only N−N bond fission, with no significant branching to N−O bond fission or NO elimination products. The translational energy distribution of the N−N bond fission products is bimodal, indicating that at least two different NO2 + NO2 product channels contribute significantly to the observed products. Both product channels have an anisotropy parameter of β = 1.7 ± 0.2. Using a Franck−Condon-like sudden analysis, we tentatively assign the two fragmentation channels observed as NO2(X2A1) + NO2(14B2/14A2) and NO2(X2A1) + NO2(22B2). To further characterize the system we present ab initio calculations (at the level of configuration interaction with single excitations) of the relevant excited states of N2O4. The data considered together with the calculations suggest a model for the product branching in which there is spin−orbit coupling in the Franck−Condon region bet...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::de1c58b822c8faf19e2776ed0d08732e https://doi.org/10.1021/jp993651u Zobrazit plný text záznamu