Matrix Isolation Study of the Interaction of Excited Neon Atoms With CCl4: Infrared Spectra of the Ion Products and of Cl2CCl. . Cl

Published

November 1, 1998

Author(s)

C Lugez, Marilyn E. Jacox, Russell D. Johnson III

Abstract

When a Ne:CCl₄ sample is codeposited at approximately 5 K with a beam of neon atoms that have been excited in a microwave discharge, the infrared spectrum of the resulting deposit includes prominent absorptions not only of CCl₃ but also of several other neutral and ionic species. The absorptions assigned to CCl₃⁺, CCl₂⁺, and CCl⁺ are consistent with previous spectroscopic identifications of these species. As at lower energies, the Cl₂ CCl .. Cl isomer of CCls₄ contributes to the product spectrum. Higher level ab initio calculations of the fundamental vibrations of this isomer and of its carbon-13 substituted counterpart give improved agreement with the experimentally observed infrared spectrum and, together with the results of a supplementary experiment, provide further support for the assignment of a structured absorption near 500 cm^-1 to this species, rather than Cl₃⁺. Uncharged Cl₂ CCl . . Cl is readily destroyed by visible radiation, with concomitant growth in the absorptions of CCl₄. Photodestruction of ionic species occurs in the ultraviolet spectral region. Evidence is presented for the stabilization of Cl₂ CCl . . Cl^- and of Cl₃CCl^- in these experiments. The latter species undergoes photodestruction in the near infrared spectral region. Two absorptions are tentatively assigned to the CCl . . Cl^- fragment ion.

Citation

Journal of Chemical Physics

Volume

109

Issue

No. 17

Pub Type

Journals

Keywords

CCl_n⁺ (n = 1-3), CCl_n^- (n = 3, 4), Cl₂CCl. . Cl, infrared spectrum, neon matrix, Penning ionization, photoionization, photoisomerization

Citation

Lugez, C. , Jacox, M. and Johnson, R. (1998), Matrix Isolation Study of the Interaction of Excited Neon Atoms With CCl₄: Infrared Spectra of the Ion Products and of Cl₂CCl. . Cl, Journal of Chemical Physics (Accessed April 28, 2024)