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Threshold photoelectron photoion coincidence spectroscopy of trichloroethene and tetrachloroethene

Parkes, M. A. and Ali, S. and Simpson, M. J. and Tuckett, R. P. and Malins, A. E. R. (2008) Threshold photoelectron photoion coincidence spectroscopy of trichloroethene and tetrachloroethene. Molecular Physics, 106 (14). pp. 1739-1749. ISSN 0026-8976

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URL of Published Version: http://www.tandfonline.com/doi/abs/10.1080/00268970802270075

Identification Number/DOI: doi:10.1080/00268970802270075

The threshold photoelectron, the threshold photoelectron photoion coincidence and ion breakdown spectra of trichloroethene and tetrachloroethene have been recorded from 9 – 22 eV. Comparisons with the equivalent data for the three dichloroethene molecules and theoretical calculations highlight the nature of the orbitals involved during photoionisation in this energy range. The ground electronic state of C$$_2$$HCl$$_3^+$$ (C$$_2$$Cl$$_4^+$$) is bound, with excited valence states dissociating to C$$_2$$HCl$$_2^+$$ (C$$_2$$Cl$$_3^+$$) and C$$_2$$HCl$$^+$$ (C$$_2$$Cl$$_2^+$$). Appearance energies suggest that C$$_2$$HCl$$^+$$ forms from C$$_2$$HCl$$_3^+$$ by loss of two chlorine atoms, whereas C$$_2$$Cl$$_2^+$$ forms from C$$_2$$Cl$$_4^+$$ by loss of a Cl$$_2$$ molecule. The translational kinetic energy release into C$$_2$$HCl$$_2^+$$ (C$$_2$$Cl$$_3^+$$) + Cl is determined as a function of energy. In both cases, the fraction of the available energy released into translational energy of the two products decreases as the photon energy increases.

Type of Work: Article 2008 (Publication) Schools (1998 to 2008) > School of Chemical Sciences School of Chemistry QD ChemistryQC Physics University of Birmingham Taylor & Francis 765 YES

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