Density functional computational thermochemistry:: solving the discrepancy between MO and DFT calculations on the enthalpy of formation of sulfine, CH2=S=O

The enthalpy of formation of sulfine is computed at the density functional (DFT) level to solve the discrepancy between previously recommended theoretical values. In agreement with the most recent CBS-QB3 calculations. which predict a value of -30 +/- 6 kJ/mol. DFT calculations on isodesmic reactions predict a value of -38 +/- 10 kJ/mol. Previous estimations of -9 +/- 14 kJ/mol (at the MO level) and -52 +/- 10 kJ/mol (at the DFT level) are discussed and shown to be artifacts of the methods of calculation employed. (C) 2002 Published by Elsevier Science B.V.