The performance of the rapid estimation of basis set error and correlation energy from partial charges method on new molecules of the G3/99 test set

S. Kristyán, Adrienn Ruzsinszky, G. Csonka

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Abstract

Experimental enthalpies of formation have been approximated using single-point Hartree-Fock (HF)-self-consistent-field (SCF) total energies plus the rapid estimation of basis set error and correlation energy from partial charges (REBECEP) energy corrections. The energy corrections are calculated from the HF-SCF partial atomic charges and optimized atomic energy parameters. The performance of the method was tested on 51 closed-shell neutral molecules (50 molecules from the G3/99 thermochemistry database plus urea, composed of H, C, N, O, and F atoms). The predictive force of the method is demonstrated, because these larger molecules were not used for the optimization of the atomic parameters. We used the earlier RECEP-3 [HF/ 6-311+G(2d,p)] and REBECEP [HF/6-31G(d)] atomic parameter sets obtained from the G2/97 thermochemistry database (containing small molecules) together with natural population analysis and Mulliken partial charges. The best results were obtained using the natural population analysis charges, although the Mulliken charges also provide useful results. The root-mean-square deviations from the experimental enthalpies of formation for the selected 51 molecules are 1.15, 3.96, and 2.92 kcal/mol for Gaussian-3, B3LYP/6-11+ G(3df,2p), and REBECEP (natural population analysis) enthalpies of formation, respectively (the corresponding average absolute deviations are 0.94, 7.09, and 2.27 kcal/ mol, respectively). The REBECEP method performs considerably better for the 51 test molecules with a moderate 6-31G(d) basis set than the B3LYP method with a large 6-311+G(3df,2p) basis set.

Original languageEnglish
Pages (from-to)404-411
Number of pages8
JournalTheoretical Chemistry Accounts
Volume106
Issue number6
DOIs
Publication statusPublished - Nov 2001

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Molecules
Thermochemistry
molecules
Enthalpy
thermochemistry
enthalpy
energy
self consistent fields
deviation
Nuclear energy
nuclear energy
Urea
ureas
Atoms
optimization
atoms

Keywords

  • B3LYP method
  • Energy parameters
  • Enthalpies of formation
  • G3 method
  • Partial charges

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "The performance of the rapid estimation of basis set error and correlation energy from partial charges method on new molecules of the G3/99 test set",
abstract = "Experimental enthalpies of formation have been approximated using single-point Hartree-Fock (HF)-self-consistent-field (SCF) total energies plus the rapid estimation of basis set error and correlation energy from partial charges (REBECEP) energy corrections. The energy corrections are calculated from the HF-SCF partial atomic charges and optimized atomic energy parameters. The performance of the method was tested on 51 closed-shell neutral molecules (50 molecules from the G3/99 thermochemistry database plus urea, composed of H, C, N, O, and F atoms). The predictive force of the method is demonstrated, because these larger molecules were not used for the optimization of the atomic parameters. We used the earlier RECEP-3 [HF/ 6-311+G(2d,p)] and REBECEP [HF/6-31G(d)] atomic parameter sets obtained from the G2/97 thermochemistry database (containing small molecules) together with natural population analysis and Mulliken partial charges. The best results were obtained using the natural population analysis charges, although the Mulliken charges also provide useful results. The root-mean-square deviations from the experimental enthalpies of formation for the selected 51 molecules are 1.15, 3.96, and 2.92 kcal/mol for Gaussian-3, B3LYP/6-11+ G(3df,2p), and REBECEP (natural population analysis) enthalpies of formation, respectively (the corresponding average absolute deviations are 0.94, 7.09, and 2.27 kcal/ mol, respectively). The REBECEP method performs considerably better for the 51 test molecules with a moderate 6-31G(d) basis set than the B3LYP method with a large 6-311+G(3df,2p) basis set.",
keywords = "B3LYP method, Energy parameters, Enthalpies of formation, G3 method, Partial charges",
author = "S. Kristy{\'a}n and Adrienn Ruzsinszky and G. Csonka",
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T1 - The performance of the rapid estimation of basis set error and correlation energy from partial charges method on new molecules of the G3/99 test set

AU - Kristyán, S.

AU - Ruzsinszky, Adrienn

AU - Csonka, G.

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N2 - Experimental enthalpies of formation have been approximated using single-point Hartree-Fock (HF)-self-consistent-field (SCF) total energies plus the rapid estimation of basis set error and correlation energy from partial charges (REBECEP) energy corrections. The energy corrections are calculated from the HF-SCF partial atomic charges and optimized atomic energy parameters. The performance of the method was tested on 51 closed-shell neutral molecules (50 molecules from the G3/99 thermochemistry database plus urea, composed of H, C, N, O, and F atoms). The predictive force of the method is demonstrated, because these larger molecules were not used for the optimization of the atomic parameters. We used the earlier RECEP-3 [HF/ 6-311+G(2d,p)] and REBECEP [HF/6-31G(d)] atomic parameter sets obtained from the G2/97 thermochemistry database (containing small molecules) together with natural population analysis and Mulliken partial charges. The best results were obtained using the natural population analysis charges, although the Mulliken charges also provide useful results. The root-mean-square deviations from the experimental enthalpies of formation for the selected 51 molecules are 1.15, 3.96, and 2.92 kcal/mol for Gaussian-3, B3LYP/6-11+ G(3df,2p), and REBECEP (natural population analysis) enthalpies of formation, respectively (the corresponding average absolute deviations are 0.94, 7.09, and 2.27 kcal/ mol, respectively). The REBECEP method performs considerably better for the 51 test molecules with a moderate 6-31G(d) basis set than the B3LYP method with a large 6-311+G(3df,2p) basis set.

AB - Experimental enthalpies of formation have been approximated using single-point Hartree-Fock (HF)-self-consistent-field (SCF) total energies plus the rapid estimation of basis set error and correlation energy from partial charges (REBECEP) energy corrections. The energy corrections are calculated from the HF-SCF partial atomic charges and optimized atomic energy parameters. The performance of the method was tested on 51 closed-shell neutral molecules (50 molecules from the G3/99 thermochemistry database plus urea, composed of H, C, N, O, and F atoms). The predictive force of the method is demonstrated, because these larger molecules were not used for the optimization of the atomic parameters. We used the earlier RECEP-3 [HF/ 6-311+G(2d,p)] and REBECEP [HF/6-31G(d)] atomic parameter sets obtained from the G2/97 thermochemistry database (containing small molecules) together with natural population analysis and Mulliken partial charges. The best results were obtained using the natural population analysis charges, although the Mulliken charges also provide useful results. The root-mean-square deviations from the experimental enthalpies of formation for the selected 51 molecules are 1.15, 3.96, and 2.92 kcal/mol for Gaussian-3, B3LYP/6-11+ G(3df,2p), and REBECEP (natural population analysis) enthalpies of formation, respectively (the corresponding average absolute deviations are 0.94, 7.09, and 2.27 kcal/ mol, respectively). The REBECEP method performs considerably better for the 51 test molecules with a moderate 6-31G(d) basis set than the B3LYP method with a large 6-311+G(3df,2p) basis set.

KW - B3LYP method

KW - Energy parameters

KW - Enthalpies of formation

KW - G3 method

KW - Partial charges

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