Density functional computational thermochemistry: determination of the enthalpy of formation of sulfine, CH2SO, at room temperature

Abstract Density functional and coupled-cluster calculations using Pople's basis sets up to 6-311++G(3df,2pd) have been employed to determine the heat of formation of sulfine, CH 2 SO, 1 , using the isodesmic reaction CH 2 S + SO 2 ⇌ CH 2 SO + SO . Other reactions, employed previously to determine the enthalpy of formation of sulfine at the CAS-SDCI/ CASSCF ab initio level, were used as well. The analysis of the results shows that: (a) the errors in the calculation of the enthalpies for the individual molecules do cancel reasonably only for the isodesmic reaction, and not for those used previously; (b) density functional methods produce smaller errors than CCSDT in the calculation of the enthalpies of formation of the molecules involved in this reaction; (c) the actual heat of formation of sulfine is determined as Δ f H o 298.15 ( 1 )=−52±10 kJ/mol, more in agreement with the prediction of Benson than with the ab initio value derived by Ruttink et al.; (d) the proton affinity of sulfine, calculated at the density functional level (792.0 kJ/mol) agrees reasonably well with the experimental result, 787.6±2.6 kJ/mol, but the enthalpy of formation of 1 derived from this proton affinity using the assumptions of Ruttink or Bouchoux is in disagreement with the value determined previously.