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Photodissociation of 1,2-chloroiodoethane at 248 and 266 nm: The enthalpy of formation of CH/sub 2/ClCH/sub 2/I

Journal Article · · J. Chem. Phys.; (United States)
OSTI ID:6672190

The technique of photofragmentation translational spectroscopy has been utilized to study the photodissociation of CH/sub 2/ClCH/sub 2/I at excitation wavelengths of 248 and 266 nm. The primary photofragments are C/sub 2/H/sub 4/Cl and either I*(/sup 2/P/sub 1//sub ///sub 2/) or I(/sup 2/P/sub 3//sub ///sub 2/). A fraction of the chloroethyl radical product contains enough internal excitation after the primary process to undergo secondary dissociation into C/sub 2/H/sub 4/ and Cl. By observing the threshold for this secondary process, the reaction enthalpy for CH/sub 2/ClCH/sub 2/I..-->..C/sub 2/H/sub 4/+Cl+I was determined, which leads to: ..delta..H/sup 0//sub f/,0 (CH/sub 2/ClCH/sub 2/I) = -7.8 +- 1 kcal/mol. The c. m. translational energy distribution of the photofragments was derived for both the I* and I channels, yielding I*/I branching ratios of 1.5 at 248 nm and 3 at 266 nm. The translational energy distribution also revealed that about 50% of the excess energy went into translation. The angular distributions of dissociation products with respect to the laser polarization indicate that the primary photodissociation process for the ground and excited state iodine channels at both wavelengths proceeds via a parallel transition, i.e., the transition moment must be nearly parallel to the C--I bond.

Research Organization:
Materials and Molecular Research Division, Lawrence Berkeley Laboratory and Department of Chemistry, University of California, Berkeley, California 94720
DOE Contract Number:
AC03-76SF00098
OSTI ID:
6672190
Journal Information:
J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 81:4; ISSN JCPSA
Country of Publication:
United States
Language:
English