Benchmarking Semiempirical Methods for Thermochemistry, Kinetics, and Noncovalent Interactions: OMx Methods Are Almost As Accurate and Robust As DFT-GGA Methods for Organic Molecules.

Abstract

Semiempirical quantum mechanical (SQM) methods offer a fast approximate treatment of the electronic structure and the properties of large molecules. Careful benchmarks are required to establish their accuracy. Here, we report a validation of standard SQM methods using a subset of the comprehensive GMTKN24 database for general main group thermochemistry, kinetics, and noncovalent interactions, which has recently been introduced to evaluate density functional theory (DFT) methods ( J. Chem. Theory Comput. 2010 , 6 , 107 ). For all SQM methods considered presently, parameters are available for the elements H, C, N, and O, and consequently, we have extracted from the GMTKN24 database all species containing only these four elements (excluding multireference cases). The resulting GMTKN24-hcno database has 370 entries (derived from 593 energies) compared with 715 entries (derived from 1033 energies) in the original GMTKN24 database. The current benchmark covers established standard SQM methods (AM1, PM6), more recent approaches with orthogonalization corrections (OM1, OM2, OM3), and the self-consistent-charge density functional tight binding method (SCC-DFTB). The results are compared against each other and against DFT results using standard functionals. We find that the OMx methods outperform AM1, PM6, and SCC-DFTB by a significant margin, with a substantial gain in accuracy especially for OM2 and OM3. These latter methods are quite accurate even in comparison with DFT, with an overall mean absolute deviation of 6.6 kcal/mol for PBE and 7.9 kcal/mol for OM3. The OMx methods are also remarkably robust with regard to the unusual bonding situations encountered in the "mindless" MB08-165 test set, for which all other SQM methods fail badly.