Velocity map imaging of the photodissociation of CF{sub 3}I : vibrational energy dependence of the recoil anisotropy.
The photodissociation of jet-cooled CF{sub 3}I into CF{sub 3{sup +}}I({sup 2}P{sub 3/2}) and CF{sub 3{sup +}}I*({sup 2}P{sub 1/2}) has been investigated between 304 and 277 nm by using velocity map ion imaging. The two-dimensional images provide detailed information on the partition of available energy into kinetic and internal energy of the photofragments. Vibrational structure with spacing of 695{+-}100cm{sup -1} is resolved in both I and I* images, indicating excitation of the umbrella mode {nu}{sub 2} of the CF{sub 3} photofragment. The fragment recoil anisotropies {beta}(I) and {beta}(I*) are determined as a function of the excitation wavelength and their variations are interpreted in terms of the crossing between the {sup 3}Q{sub 0} and {sup 1}Q{sub 1} dissociative electronic states. The high-resolution images allow the determination of the variation of the anisotropy parameter {beta} as a function of the vibrational level of CF{sub 3} fragment, and provide a complementary method for the determination of the C-I bond energy. The vibrational dependence of the anisotropy values is discussed in terms of final-state interactions between the CF{sub 3} umbrella motion and the C-I dissociation coordinate, as discussed previously by Henning et al. [J. Chem. Phys. 84, 544 (1986)].
- Research Organization:
- Argonne National Laboratory (ANL)
- Sponsoring Organization:
- SC
- DOE Contract Number:
- AC02-06CH11357
- OSTI ID:
- 961081
- Report Number(s):
- ANL/CHM/JA-44442
- Journal Information:
- J. Chem. Phys., Journal Name: J. Chem. Phys. Journal Issue: 3 ; Jan. 15, 2003 Vol. 118; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- ENGLISH
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