Energy Correctors for Accurate Prediction of Molecular Energies Academic Article uri icon

abstract

  • Energy correctors are introduced for the calculation of molecular energies of compounds containing first row atoms (Li-F) to modify ab initio molecular orbital calculations of energies to better reproduce experimental results. Four additive correctors are introduced to compensate for the differences in the treatment of molecules with different spin multiplicities and multiplicative correctors are also calculated for the electronic and zero-point vibrational energies. These correctors, individually and collectively yield striking improvements in the atomization energies for several ab initio methods. We use as training set the first row subset of molecules from the G1 basis of molecules; when the correctors are applied to other molecules not included in the training set, selected from the G3 basis, similar improvements in the atomization energies are obtained. The special case of the B3PW91/cc-pVTZ yields an average error of 1.2 kcal/mol, which is already within a chemical accuracy and comparable to the Gaussian-n theories accuracy. The very inexpensive B3PW91/6-31G** yields an average error of 2.1 kcal/mol using the correctors. Methods considered unsuitable for energetics such as HF and LSDA yield corrected energies comparable to those obtained with the best highly correlated methods.

author list (cited authors)

  • Seminario, J. M., Maffei, M. G., Agapito, L. A., & Salazar, P. F.

publication date

  • January 1, 2005 11:11 AM