Journal of Physical Chemistry A, Vol.102, No.45, 9031-9039, 1998
Systematic errors in ab initio bond dissociation energies
Bond dissociation energies (D-0) for 41 small molecules were calculated at 19 levels of ab initio theory up to CCSD(T)/cc-pVTZ, using geometries and vibrational zero-point energies from B3LYP/6-31G* hybrid density-functional calculations. Empirical correlations between the errors in the ab initio bond strengths and the following quantities were examined : (1) the distance between the bonded atoms, (2) the electron density at the midbond critical point, and (3) the contribution of dynamic electron correlation to the bond strength. Correlation 1 is related to the BAC-MP4 method of Melius and co-workers, and correlation 3 corresponds to the SAC methods of Truhlar, Gordon, and co-workers and to the PCI methods of Siegbahn, Blomberg, and co-workers. For each type of empirical correction, empirical estimates of the standard uncertainty for an arbitrary prediction are also provided. Type 3 correlations fail for bonds involving second-row elements (e.g. : silicon), suggesting that the cc-pVTZ basis sets are not correlation balanced across the different periods. For the lighter elements, however, all three corrections are effective and could be refined into prescriptive methods.
Keywords:DENSITY-FUNCTIONAL THEORY, QUADRATIC CONFIGURATION-INTERACTION;GAUSSIAN-BASIS SETS, CORRELATED MOLECULAR CALCULATIONS, TOTALATOMIZATION ENERGIES, ELECTRON CORRELATION, HALONTHERMOCHEMISTRY, PERTURBATION-THEORY, SPIN CONTAMINATION, ATOMEQUIVALENTS