In:
The Journal of Chemical Physics, AIP Publishing, Vol. 130, No. 18 ( 2009-05-14)
Kurzfassung:
Br 2 molecular elimination is probed in the photodissociation of 1,1- and 1,2-C2H4Br2 isomeric forms at 248 nm by using cavity ring-down absorption spectroscopy. Their photodissociation processes differ markedly from each other. The quantum yield of the Br2 fragment in 1,2-dibromoethane is 0.36±0.18, in contrast to a value of 0.05±0.03 in 1,1-dibromoethane. The vibrational population ratios of Br2(v=1)/Br2(v=0) are 0.8±0.1 and 0.5±0.2 for 1,2- and 1,1-dibromoethanes, respectively. The Br2 yield densities are found to increase by a factor of 35% and 190% for 1,2- and 1,1-dibromoethanes within the same temperature increment. In the ab initio potential energy calculations, the transition state (TS) along the adiabatic ground state surface may correlate to the Br2 products. The TS energy for 1,2-dibromoethane is well below the excitation energy at 483 kJ/mol, whereas that for 1,1-dibromoethane is slightly above. Such a small TS energy barrier impedes the photodissociation of the ground state 1,1-dibromoethane such that the production yield of Br2 may become relatively low, but rise rapidly with the temperature. The TS structure shows a larger bond distance of Br–Br in 1,2-dibromoethane than that in 1,1-dibromoethane. That explains why the former isomer may result in hotter vibrational population of the Br2 fragments.
Materialart:
Online-Ressource
ISSN:
0021-9606
,
1089-7690
Sprache:
Englisch
Verlag:
AIP Publishing
Publikationsdatum:
2009
ZDB Id:
3113-6
ZDB Id:
1473050-9
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