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Calibration and comparison of the Gaussian-2, complete basis set, and density functional methods for computational thermochemistry

J. Chem. Phys. 109, 10570 (1998); doi:10.1063/1.477794

Issue Date: 22 December 1998

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G. A. Petersson, David K. Malick, and William G. Wilson
Hall-Atwater Laboratories of Chemistry, Wesleyan University, Middletown, Connecticut 06459-0180

Joseph W. Ochterski
Silicon Graphics, Inc., 100 Corporate Place, Rocky Hill, Connecticut 06067

J. A. Montgomery, Jr. and M. J. Frisch
Lorentzian, Inc., 140 Washington Ave., North Haven, Connecticut 06473
We have reexamined several high-accuracy Gaussian-2, complete basis set and density functional methods for computational thermochemistry (in order of increasing speed): G2, G2(MP2), CBS-Q, G2(MP2,SVP), CBS-q, CBS-4, and B3LYP/6-311 + G(3df,2p). We have employed DeltafH<sub>298</sub><sup>0</sup> for the "extended G2 neutral test set" for this comparison. Several errors in previous studies have been corrected and experimental spin-orbit interactions have been included in all calculated atomic energies. The mean absolute deviations from experiment are 1.43, 1.76, 1.19, 1.64, 2.34, 2.66, and 3.43 kcal/mol, respectively. The maximum deviations from experiment are 10.6, 8.8, 8.1, 9.4, 11.4, 12.9, and 24.1 kcal/mol respectively. The species responsible for these maximum errors are in order: SiF4, SiF4, Cl2C[Double Bond]CCl2, F2C[Double Bond]CF2, ClF3, ClF3, and SiCl4. All seven methods have relatively large errors for bonds to halogens, but these errors are sufficiently systematic to benefit from empirical corrections. After a discussion of ill conditioning in the "bond separation reaction" implementation of isodesmic reactions, we determine "isodesmic bond additivity corrections" (BACs) for several types of bonds by least-squares fits to the heats of formation for 76 organic species with up to ten carbons and a variety of heteroatoms. The mean absolute deviations are reduced from 1.49, 1.93, 1.22, 1.53, 2.28, 3.09, and 3.45 kcal/mol to 0.55, 0.57, 0.77, 0.63, 1.03, 0.98, and 1.16 kcal/mol. The maximum errors are reduced to about 3 kcal/mol for all but the DFT method (4.2 kcal/mol). The BACs are especially useful for larger molecules with many similar bonds. For example, the CBS-Q error for Cl2C[Double Bond]CCl2 is reduced from 8.1 to 3.0 kcal/mol and the CBS-4 errors for benzene and naphthalene are reduced from 10.5 and 17.5 to 2.1 and 1.6 kcal/mol, respectively. ©1998 American Institute of Physics.
History: Received 16 July 1998; accepted 21 September 1998
Permalink: http://link.aip.org/link/?JCPSA6/109/10570/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.60.-s
    Physical chemistry Chemical thermodynamics
  • 31.15.Ew
    Electronic structure of atoms, molecules and their ions: theory Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) Density-functional theory
  • YEAR: 1998

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0021-9606 (print)   1089-7690 (online)
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