Abstract
Photodissociation mass spectra and mass selected (1+1)-photodissociation spectra of C2H5I+*, C2D5I+*, 1-C3H7I+*, 2-C3H7I+*, 1-C4H9I+* and 2-C4H9I+* radical cations were studied within the à ← X˜ absorption band. The photodissociation mass spectra within the range 13,600–15,900 cm−1 (1.68–1.97 eV) display only a simple cleavage of the C–I bond and formation of the corresponding alkyl ions. The resonant (1+1)-photodissociation spectra of C2H5I+* and C2D5I+* show intense vibrational structure in the excited à state. The thresholds for formation of the à states of C2H5I+ and C2D5I+ were estimated to be (13,278 ± 12) cm−1 (1.6462 ± 0.0014 eV) and (13,363 ± 12) cm−1 (1.6586 ± 0.0014 eV), respectively. Whereas a few resonant vibrational excitations could be identified with 1-C3H7I+* and 1-C4H7I+, no vibrational features were observable with 2-C3H7I+* and 2-C4H9I+*. It is concluded that 1- and 2-iodoalkane radical cations do not rearrange, even under the conditions of electron ionisation used to generate the molecular ions.
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