Summary: Bond-based corrections to semi-empirical and ab initio
electronic structure calculations
David A. Long a
, James B. Anderson b,*
Department of Chemistry, Kenyon College, Gambier, OH 43022, USA
Department of Chemistry and Department of Physics, Pennsylvania State University, University Park, 104 Chemistry Building,
Pennsylvania, PA 16802, USA
Received 15 November 2004; in final form 22 December 2004
Available online 8 January 2005
A simple, empirical, bond-based correction method improves the accuracy of several types of electronic structure calculations in
predicting heats of formation. The optimal corrections for common types of bonds are determined by minimizing the deviations
from experimental thermochemical data. The method is tested with the 223-species of the G3/99 test set of Curtiss et al. For the
subset of 155 species containing only bonds in the set of 15 bonds for which corrections are made, the mean absolute error is reduced
from 142 to 1.84 for LSDA, from 0.81 to 0.61 for G3, from 4.65 to 1.48 for B3LYP, from 5.54 to 1.94 for TPSS, and from 3.51 to
1.76 for TPSSh (all in kcal/mol).
Ó 2004 Elsevier B.V. All rights reserved.