A comparative study of the singlet-triplet energy separation of carbenes using density functional theory and coupled-cluster methods

The singlet-triplet energy separation (Delta ES-T) of carbenes has been stu died using density functional theory (DFT) and the single, double, plus per turbative triple excitations coupled-cluster {CCSD(T)} approaches. Delta ES -T predictions from DFT were compared with those of CCSD(T). We found that BLYP and G96LYP predictions are closest to the CCSD(T) results, with the av erage absolute deviations within 1 kcal/mol. Many of the tested functionals overestimate Delta ES-T. It was observed that best comparisons are display ed by the choice of correlation (LYP) functionals, while the effect of choo sing among exchange functionals is less significant. The hybrid functionals provide poorer, overestimated predictions for Delta ES-T. (C) 1999 Elsevie r Science B.V. All rights reserved.