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Issue 32, 2016
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The methylsulfinyl radical CH3SO examined

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Abstract

Methylsulfinyl radical, a key intermediate in marine atmospheric chemistry, plays a central role in the oxidation of dimethyl sulfide. CH3SO has been extensively studied here with ab initio quantum mechanical methods, with methods as complete as CCSDT(Q) in conjunction with basis sets as large as cc-pV(5+d)Z. In this research, we report high-level computations for the ground and first excited electronic states of the methylsulfinyl radical. The structures of the [X with combining tilde] 2A′′ and à 2A′ states are quite different with S–O distances of 1.499 and 1.652 Å, respectively. The [X with combining tilde] to à adiabatic energy difference is predicted to be 45.1 kcal mol−1, compared to 21.1 kcal mol−1 for the analogous well-characterized methylperoxy radical CH3OO. The CH3SO barrier to internal rotation is 0.92 kcal mol−1. The unknown [X with combining tilde] 2A′′ torsional vibrational frequency τ is predicted to be 142 cm−1 (harmonic) and 128 cm−1 (anharmonic). Our predictions of the à 2A′ excited state vibrational frequencies are the first to be reported.

Graphical abstract: The methylsulfinyl radical CH3SO examined

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The article was received on 27 Jun 2016, accepted on 20 Jul 2016 and first published on 21 Jul 2016


Article type: Paper
DOI: 10.1039/C6CP04505G
Citation: Phys. Chem. Chem. Phys., 2016,18, 22293-22299
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    The methylsulfinyl radical CH3SO examined

    M. L. Estep and H. F. Schaefer III, Phys. Chem. Chem. Phys., 2016, 18, 22293
    DOI: 10.1039/C6CP04505G

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