The Vibrational Spectra of Molecular Ions Isolated in Solid Neon. XVI. SO+2, SO-2, and (SO2)-2

Published

July 1, 2000

Author(s)

D Forney, C B. Kellogg, Warren E. Thompson, Marilyn E. Jacox

Abstract

When a Ne:SO₂ mixture is subjected to Penning ionization and/or photoionization by neon atoms in their first excited states, between 16.6 eV and 16.85 eV, and the products are rapidly frozen at approximately 5 K, the infrared spectrum of the resulting deposit includes absorptions assigned with the aid of isotopic substitution studies to SO, SO₂⁺, SO₂ , (SO₂)₂ , and, tentatively, SO . The fundamental and first overtone absorptions of SOlie 0.9 cm^-1 and 1.8 cm^-1, respectively, below the gas-phase band centers. Ab initio calculations at the Hartree-Fock level show an instability in the Ņ₃ and Ņ₁ fundamentals of SO₂ isolated in solid neon are identified at 1086.2 cm^-cm-1 and 990.8 cm^-1, respectively. In agreement with an earleir proposal, the 1042^-1 absorption originally assigned to Ņ₃ of SO₂ trapped in solid argon is reassigned to MSO₂ with M an alkali metal. Near the photodetachment threshold for SO₂ isolated in a neon matrix, electron capture by SO₂ nearest neighbor pairs results in growth of infrared absorptions of (SO₂)₂ , which has been shown by gas-phase studies to have a significantly higher photodetachment threshold than doesSO₂ . The isotopic substitution studies require that the two sulfur atoms in (SO₂)₂ be nonequivalent, favoring the linking of the two SO₂ units by a S...O bond.

Citation

Journal of Chemical Physics

Volume

113

Issue

No. 1

Pub Type

Journals

Keywords

(SO₂)₂, ab initio calculations, infrared spectrum, neon matrix, photoionization, SO, SO, SO₂, SO₂⁺

Citation

Forney, D. , Kellogg, C. , Thompson, W. and Jacox, M. (2000), The Vibrational Spectra of Molecular Ions Isolated in Solid Neon. XVI. SO⁺₂, SO^-₂, and (SO₂)^-₂, Journal of Chemical Physics (Accessed October 14, 2025)