A simple composite scheme is presented and benchmarked against the 38 reactions in Truhlar's HTBH38/08 and NHTBH38/08 databases. Mean unsigned deviation (MUD) for the complete set of 68 independent barriers is 0.40 kcal mol À1 , compared to 1.31 kcal mol À1 for G4 and 1.62 kcal mol À1 for the M06-2X-D3 method. The MUD of the new scheme on the barriers in the DBH24/08 subset (12 out of the 38 reactions in the other sets) is 0.27 kcal mol À1 , better than that obtained at the expensive CCSD(T,full)/aug-cc-pCV(T+d)Z level (0.46 kcal mol À1 ) and comparable to the most exact (and costly) Wn calculations (MUD = 0.14 kcal mol À1 ). The method was further tested against a subset of reactions, for which the geometry and energies of all species were determined at the much more demanding CCSD(T)-F12//pVQZ-F12 level. The SVECV-f12 procedure on this database results in RMSE and MUD values of only 0.21 and 0.16 kcal mol À1 .

No abstract

In a previous work, we have investigated the initial steps of the reaction of toluene with the hydroxyl radical using several quantum chemical approaches including density functional and composite post-Hartree–Fock models. Comparison of H-abstraction from the methyl group and additions at different positions of the phenyl ring showed that the former reaction channel is favored at room temperature. This conclusion appears at first sight incompatible with the experimental observation of a lower abundance of the product obtained from abstraction (benzaldehyde) with respect to those originating from addition (cresols). Further reactions of the intermediate radicals with oxygen, water, and additional OH radicals are explored in this paper through theoretical calculations on more than 120 species on the corresponding potential energy surface. The study of the addition reactions, to obtain the cresols through hydroxy methylcyclodienyl intermediate radicals, showed that only in the case of o -cresol the reaction proceeds by addition of O 2 to the ring, internal H-transfer, and hydroperoxyl abstraction and not through direct H-abstraction. For both p - and m -cresol, instead, the reaction occurs through a higher-energy direct H-abstraction, thus explaining in part the observed larger concentration of the ortho isomer in the final products. It was also found that the benzyl radical, formed by H-abstraction from the methyl group, is able to react further if additional OH is present. Two reaction paths leading to o -cresol, two leading to p -cresol, and one leading to m -cresol were determined. Moreover, in this situation, the benzyl radical is predicted to produce benzyl alcohol, as was found in some experiments. The commonly accepted route to benzaldehyde was found to be not the energetically favored one. Instead, a route leading to the benzoyl radical (and ultimately to benzoic acid) with the participation of one water molecule was clearly more favorable, both thermodynamically and kinetically.

No abstract

Thione S-methylide, parent species of the thiocarbonyl ylide family, is a 1,3dipolar species on the [C 2 SH 4 ] potential energy surface, not so much studied as its isomers, thiirane, vinyl thiol, and thioacetaldehyde. The conrotatory ring-closure reaction toward thiirane was studied in the 90s, but no complete analysis of the potential energy surface is available. In this paper, we report a computational study of the reaction scheme linking all species. We employed several computational methods (density functional theory, CCSD(T) composite schemes, and CASSCF/CASPT2 multireference procedures) to find the best description of thione S-methylide, its isomers, and transition states. The barrier from thiirane to thione Smethylide amounts to 52.2 kcal mol −1 (against 17.6 kcal mol −1 for the direct one), explaining why thiocarbonyl ylides cannot be prepared from thiiranes. Conversion of thiirane to vinyl thiol implies a large barrier, supporting why the reaction has been observed only at high temperatures. Fragmentations of thiirane to S( 3 P) or S( 1 D) and ethylene as well as decomposition to hydrogen sulfide plus acetylene were also explored. Triplet and singlet open-shell species were identified as intermediates in the fragmentations, with energies lower than the transition state between thiirane and vinyl thiol, explaining the preference of the latter at low temperatures.