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Abstract
Laser-ion beam photodissociation is used to study the C4H+6 radical cation formed by electron impact (70 eV nominal energy) ionization of 1,3-butadiene. The kinetic energy release value obtained from C4H+6→C3H+3+CH3 does not agree with the distribution reported by Farrar [J. Chem. Phys. 77, 263 (1982)]. The photodissociation studies of C4H+6 suggest the existence of a long-lived (>0.05×10−6 s) photoexcited C4H+6 ion. Also, results of photodissociation studies of C4H+6 trapped in the electron beam space charge are consistent with the proposed long-lived photoexcited C4H+6 ion. Therefore, it is proposed that the two-photon photodissociation of C4H+6 reported by Baer [J. Chem. Phys. 85, 6361 (1986)] is a sequential two-step process involving a long-lived excited C4H+6 ion.
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