The Vibrational Spectra of Molecular Ions Isolated in Solid Neon. XVI. SO+2, SO-2, and (SO2)-2
D Forney, C B. Kellogg, Warren E. Thompson, Marilyn E. Jacox
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.
Journal of Chemical Physics
(SO<sub>2</sub>)<sub>2</sub>, ab initio calculations, infrared spectrum, neon matrix, photoionization, SO, SO, SO<sub>2</sub>, SO<sub>2</sub><sup>+</sup>
, Kellogg, C.
, Thompson, W.
and Jacox, M.
The Vibrational Spectra of Molecular Ions Isolated in Solid Neon. XVI. SO<sup>+</sup><sub>2</sub>, SO<sup>-</sup><sub>2</sub>, and (SO<sub>2</sub>)<sup>-</sup><sub>2</sub>, Journal of Chemical Physics
(Accessed June 2, 2023)