Isomers of S2O: Infrared absorption spectra of cyclic S2O in solid Ar

Details Isomers of S2O: Infrared absorption spectra of cyclic S2O in solid Ar Isomers of S2O: Infrared absorption spectra of cyclic S2O in solid Ar

Oct 2002

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2002jchph.117.6655l&link_type=abstract

Journal of Chemical Physics, Volume 117, Issue 14, pp. 6655-6661 (2002).

Physics

Chemical Physics

11

Infrared Spectra, Processes Caused By Visible And Uv Light, Isomerization And Rearrangement, Potential Energy Surfaces For Chemical Reactions

Scientific paper

Disulfur oxide (denoted as SSO) isolated in solid Ar at 13 K was irradiated with light at 308 nm from a XeCl excimer laser. New lines at 799.1 (797.0), 574.9, and 544.1 (545.6) cm-1, observed after photolysis, are assigned to cyclic S2O (denoted Cyc-S2O) with angupr S-O-S≅72.5+/-3.0° based on results of 34S- and 18O-isotopic experiments; lines in parentheses are associated with a minor matrix site and the broad line at 574.9 cm-1 may be deconvoluted to two lines at 575.4 and 574.6 cm-1. Secondary photolysis at 248 nm diminishes lines of cyc-S2O and produces SSO. Theoretical calculations using second-order Møller-Plesset theory with frozen core gradients and density-functional theories (Becke's exchange functional with a correlation functional of Lee, Yang, and Parr) predict three stable isomers of S2O: cyc-S2O, SSO, and SOS, with the latter two having angular geometry. Relative energies, structures, vibrational wave numbers, and IR intensities were predicted for each isomer. According to calculations with Becke's three-parameter exchange functional and the valence triplet-ζ basis set, cyc-S2O is bent with angupr S-O-S≅73.3° and has the S-S bond (2.058 Å) and both S-O bonds (1.724 Å) elongated relative to those of SSO (1.909 and 1.474 Å, respectively); it lies 41.3 kcal mol-1 above SSO. Isomer SOS, 62.0 kcal mol-1 greater in energy than SSO, has a S-O bond length 1.625 Å and angupr S-O-S≅128.5°. Calculated vibrational wave numbers, IR intensities, and isotopic shifts for cyc-S2O fit satisfactorily with experimental results. Two asymmetric transition states connecting SSO with SOS and cyc-S2O are characterized, yielding barriers for isomerization ~104 and 122 kcal mol-1 (zero-point energy corrected), respectively. Photoconversion between angular SSO and cyc-S2O in a matrix cage is discussed. cyc-S2O might be responsible for some distinct features in thermal emission from the surface of Io, Jupiter's moon.

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