Collect. Czech. Chem. Commun.
2000, 65, 455-476
https://doi.org/10.1135/cccc20000455
Franck-Condon Dominated Chemistry. Formation and Dissociations of the Dimethylhydroxysulfuranyl Radical
František Tureček
Department of Chemistry, Bagley Hall, Box 351700, University of Washington, Seattle, WA 98195-1700, U.S.A.
Abstract
The structure and energetics of the hydroxyl radical adduct to dimethyl sulfide (DMS) was revisited using high level ab initio calculations. Density functional theory B3LYP/6-31++G(2d,p) and perturbational MP2(FULL)/6-31++G(2d,p) calculations found a weakly bound structure, (CH3)2SOH•, with a long S-O bond that was a local energy minimum. Single point calculations at the effective QCISD(T)/6-311++G(3df,2p) level of theory, denoted as G2++(MP2), found the (CH3)2S-OH• bonding energy to be 40 kJ mol-1 at 298 K. The standard heat of formation of (CH3)2SOH• was assessed from dissociation and isodesmic reactions as -45 ± 4 kJ mol-1. No other local minima corresponding to C2H7OS radicals were found at the present level of theory that could be derived from DMS or dimethyl sulfoxide (DMSO). A very weak complex, CH3S(H)-•OCH3, was found that was bound by mere 4 kJ mol-1 against dissociation to CH3SH and •OCH3. Vertical electron capture by (CH3)2SOH+ is predicted to form (CH3)2SOH• with a highly non-relaxed geometry corresponding to a vibrational excitation of 138 kJ mol-1 above the local minimum and 88 kJ mol-1 above the dissociation threshold to DMS and OH•. Unimolecular dissociation of (CH3)2SOH• to methanesulfenic acid (CH3SOH) and •OCH3 faces an energy barrier that diminishes at shorter S-O distances. The dipole-allowed electronic excitation in (CH3)2SOH• was calculated with CIS/6-311++G(2df,p) to have λmax = 248 nm in the gas phase. The resulting B state represents a charge-transfer complex of (CH3)2S+• and OH-. The present computational results allowed us to explain the existing controversy between the experimental results obtained by gas-phase flow kinetics, radiolysis in aqueous solution, and neutralization-reionization mass spectrometry.
Keywords: Ab initio calculations; Dimethyl sulfide; Dimethyl sulfoxide; Oxidations; Radicals; Gas-phase chemistry; Mass spectrometry; Atmospheric chemistry.
References: 58 live references.
