Excitation and ionization of the monohaloethylenes (C 2H 3X, X = F, Cl, Br, I). II. Photoionization by He(I) and He(II) photoelectron spectroscopy and valence-shell excitation by electron energy loss spectroscopy

• Published in: Chemical physics Vol. 137; no. 1; pp. 369 - 390
• Main Authors: Sze, K.H., Brion, C.E., Katrib, A., El-Issa, B.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 15.10.1989; Elsevier
• Subjects: Atomic and molecular physics; Exact sciences and technology; Molecular properties and interactions with photons; Photoelectron spectra; Physics; Substituent effect; Photoelectron spectrum; Orbital interaction; Electronically excited state; Inductive effect; Experimental study; Ethylenic aliphatic compound; Electron molecule collision; Intermediate energy; Vibrational analysis; Vacuum ultraviolet radiation; Ionization potential; Excitation; Electron energy level; Electron spectrometry; Halogen Organic compounds; Energy loss spectrometry
• ISSN: 0301-0104
• DOI: 10.1016/0301-0104(89)87121-6

The He (I) and He (II) photoelectron spectra and the valence-shell electron energy loss spectra for C 2H 3X (X = F, Cl, Br and I) have been recorded. The valence-shell electron energy loss spectra were obtained at an impact energy of 3000 eV and a zero degree scattering angle. In contrast to previous studies, the HOMO orbital in C 2H 3I is reassigned with dominant iodine 5p· character rather than the π(CC) character observed for the HOMO orbitals of C 2H 3F, C 2H 3Cl and C 2H 3Br. This reordering of the assignment in C 2H 3I is based on considerations of peak shape, vibrational profile and relative intensity change between He(I) and He (II) photoelectron spectra as well as observations from the valence shell electron energy loss spectra. The valence shell electron energy loss spectrum of each of the monohaloethylenes is tentatively assigned as being due to transitions from the various occupied valence orbitals to common manifolds of π*(CC), σ-*(CX) and Rydberg final orbitals. A linear correlation between the CX bond strength and the term values of the 2a″→σ* (CX) transition is also demonstrated.