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# Fragmentation of valence electronic states of CF3-CH2F+ and CHF2-CHF2+ in the range 12-25 eV

Zhou, W. and Seccombe, D. P. and Tuckett, R. P. (2002) Fragmentation of valence electronic states of CF3-CH2F+ and CHF2-CHF2+ in the range 12-25 eV. Physical Chemistry Chemical Physics, 4 (19). pp. 4623-4633. ISSN 1463-9076

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URL of Published Version: http://dx.doi.org/10.1039/b206093k

Identification Number/DOI: doi:10.1039/b206093k

Tunable vacuum-ultraviolet radiation from a synchrotron source and threshold photoelectron-photoion coincidence spectroscopy have been used to study the decay dynamics of the valence electronic states of CF$$_3$$-CH$$_2$$F$$^+$$ and CHF$$_2$$-CHF$$_2$$$$^+$$. The threshold photoelectron spectra, fragment ion yield curves, and breakdown diagrams of CF$$_3$$-CH$$_2$$F and CHF$$_2$$-CHF$$_2$$ have been obtained in the photon energy range 12-25 eV, the electrons and fragment ions being detected by a threshold electron analyser and a linear time-of-flight mass spectrometer, respectively. For the dissociation products of (CF$$_3$$-CH$$_2$$F$$^+$$)* and (CHF$$_2$$-CHF$$_2$$$$^+$$)* formed via a single-bond cleavage, the mean translational kinetic energy releases have been measured and compared with the predictions of statistical and pure-impulsive mechanisms. Ab initio G2 calculations have determined the minimum-energy geometries of CF$$_3$$-CH$$_2$$F and CHF$$_2$$-CHF$$_2$$ and their cations, and deduced the nature of the high-lying valence orbitals of both neutral molecules. Furthermore, enthalpies of formation at 298 K of both neutral molecules, and all the neutral and fragment ions observed by dissociative photoionisation have been calculated. Combining all experimental and theoretical data, the decay mechanisms of the ground and excited valence states of CF$$_3$$-CH$$_2$$F$$^+$$ and CHF$$_2$$-CHF$$_2$$$$^+$$ are discussed. The first and second excited states of both ions show some evidence for isolated-state behaviour, with fast dissociation by cleavage of a C-F or C-H bond and a relatively large translational energy released in the two fragments. The ground state of both ions dissociate by cleavage of the central C-C bond, with a much smaller translational energy release. Several fragment ions are observed which form via H-atom migration across the C-C bond ; for h$$v$$ > 18 eV, CH$$_2$$F$$^+$$ is even the dominant ion from dissociative photoionisation of CHF$$_2$$-CHF$$_2$$. New experimental values are determined for the enthalpy of formation at 298 K of CF$$_3$$-CH$$_2$$F (-905 ± 5 kJ mol$$^{-1}$$), CHF$$_2$$-CHF$$_2$$ (-861 ± 5 kJ mol$$^{-1}$$), CF$$_2$$-CH$$_2$$F$$^+$$ ($$\leq$$ 485 ± 7 kJ mol$$^{-1}$$), CF$$_2$$-CHF$$_2$$$$^+$$ ($$\leq$$ 324 ± 7 kJ mol$$^{-1}$$) and CHF-CHF$$_2$$$$^+$$
($$\leq$$ 469 ± 7 kJ mol$$^{-1}$$).

Type of Work: Article 2002 (Publication) Schools (1998 to 2008) > School of Chemical Sciences School of Chemistry QD ChemistryQC Physics University of Birmingham The authors, Royal Society of Chemistry 753 YES

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