LASER-ION BEAM PHOTODISSOCIATION STUDIES OF C6H6+ RADICAL CATIONS - THE 2,4-HEXADIYNE SYSTEM
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The results of a laser-ion beam study of the photodissociation of C6H6+ ions are presented. In the visible wavelength range of the argon ion laser, C6H6+ ions from 2,4-hexadiyne were the only C6H6+ ions for which photodissociation was observed. The observed products were C6H5+, C6H4+, C4H4+, and C3H3+, The absorption was assigned to a 2EuX2Eg transition in the 2,4-hexadiyne cation. The photodissociation spectrum, photofragment branching ratios, information on the product relative kinetic energies, and photofragment angular distributions are presented and discussed along with the results of statistical theory model calculations. We conclude that dissociation of 2,4-hexadiyne cation 2EU proceeds by internal conversion to the ground state followed by vibrational predissociation. The relatively large anisotropy of the photofragment angular distributions indicates that isomerization to a benzene structure does not precede dissociation. 1985, American Chemical Society. All rights reserved.