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Title: Laser ionization spectroscopy of CD/sub 3/ via the 3p/sub z/ /sup 2/A''/sub 2/ Rydberg state

Journal Article · · J. Chem. Phys.; (United States)
OSTI ID:6613746

Nascent CD/sub 3/ radicals produced by photodissociation of CD/sub 3/I after absorption of 266 nm radiation by the A-italic-tilde state are studied using the photofragment imaging technique. Two-photon, resonance-enhanced, multiphoton ionization ((2+1) REMPI) probes CD/sub 3/ via the 3p/sub z/ /sup 2/A'/sub 2/ Rydberg excited electronic state. CD/sub 3/I photodissociation at 266 nm is found to produce ground-electronic-state CD/sub 3/ radicals with substantial vibrational excitation of the ..nu../sub 2/ umbrella mode. Rotational constants are determined for v = 0, 1, and 2 of ..nu../sub 2/ in the 3p/sub z/ excited state by analysis of the spectra. A first-order perturbation and diagonalization procedure is used to generate potential energy curves for the umbrella mode in both the ground and excited electronic states and Franck--Condon factors for various transitions between the states. These results should prove useful when employing REMPI to characterize methyl radicals in many environments.

Research Organization:
Department of Chemistry, University of California Santa Cruz, Santa Cruz, California 95064
OSTI ID:
6613746
Journal Information:
J. Chem. Phys.; (United States), Vol. 90:1
Country of Publication:
United States
Language:
English