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Photodissociation Dynamics of Cl2O: Interpretation of Electronic Transitions
- Source :
- The Journal of Physical Chemistry A. 108:7954-7964
- Publication Year :
- 2004
- Publisher :
- American Chemical Society (ACS), 2004.
-
Abstract
- The photodissociation of Cl 2 O has been investigated for adjacent regions in the first and the second absorption bands, respectively, at dissociation wavelengths of 5.3 and 6.0 eV. Chlorine and oxygen atoms were state;electively detected by resonance-enhanced multiphoton ionization. Chlorine fragment kinetic energy and spatial distributions were determined from time-of-flight profile analysis. At 5.3 eV, kinetic energy distributions are broad and bimodal and differ significantly for the two spin-orbit states Cl*( 2 P 1 / 2 ) and Cl( 2 P 3 / 2 ). The decay is characterized by a positive anisotropy parameter of 0.7 ′ 0.2. Excitation proceeds via the transitions 10a 1 ← 7b 2 and 10a 1 ← 9a 1 . The data are in agreement with generating CIO(X) + Cl*( 2 P 1 / 2 ) as primary fragments. At 6.0 eV. kinetic energy distributions are narrow and structureless and are similar for the two spin-orbit states Cl*(2P 1 / 2 ) and Cl( 2 P 3 / 2 ). The decay is characterized by a small positive anisotropy parameter of 0.2 ′ 0.2. The main dissociation channel is the three-body decay into 2Cl + O. The decay mechanism is of an asynchronous concerted type. The data suggest the primary production of ClO(A) + Cl( 2 P J ). Excitation proceeds mainly via the transition 8b 2 ← 7b 2 . The results show the need for refined theoretical calculations.
Details
- ISSN :
- 15205215 and 10895639
- Volume :
- 108
- Database :
- OpenAIRE
- Journal :
- The Journal of Physical Chemistry A
- Accession number :
- edsair.doi...........0d86122132261a75ed25c31a6395445f