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Title: Gaussian-4 theory using reduced perturbation orders.

Abstract

Two modifications of Gaussian-4 (G4) theory [L. A. Curtiss et al., J. Chem. Phys. 126, 084108 (2007)] are presented in which second- and third-order perturbation theories are used in place of fourth-order perturbation theory. These two new methods are referred to as G4(MP2) and G4(MP3), respectively. Both methods have been assessed on the G3/05 test set of accurate experimental data. The average absolute deviation from experiment for the 454 energies in this test set is 1.04 kcal/mol for G4(MP2) theory and 1.03 kcal/mol for G4(MP3) theory compared to 0.83 kcal/mol for G4 theory. G4(MP2) is slightly more accurate for enthalpies of formation than G4(MP3) (0.99 versus 1.04 kcal/mol), while G4(MP3) is more accurate for ionization potentials and electron affinities. Overall, the G4(MP2) method provides an accurate and economical method for thermochemical predictions. It has an overall accuracy for the G3/05 test set that is much better than G3(MP2) theory (1.04 versus 1.39 kcal/mol) and even better than G3 theory (1.04 versus 1.13 kcal/mol). In addition, G4(MP2) does better for challenging hypervalent systems such as H2SO4 and for nonhydrogen species than G3(MP2) theory.

Authors:
; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
953808
Report Number(s):
ANL/MSD/JA-59220
Journal ID: ISSN 0021-9606; JCPSA6; TRN: US201004%%567
DOE Contract Number:
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Chem. Phys.; Journal Volume: 127; Journal Issue: 2007
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; ELECTRONS; GAUSSIAN PROCESSES; IONIZATION POTENTIAL; MODIFICATIONS; PERTURBATION THEORY

Citation Formats

Curtiss, L. A., Redfern, P. C., Raghavachari, K., and Indiana Univ.. Gaussian-4 theory using reduced perturbation orders.. United States: N. p., 2007. Web. doi:10.1063/1.2770701.
Curtiss, L. A., Redfern, P. C., Raghavachari, K., & Indiana Univ.. Gaussian-4 theory using reduced perturbation orders.. United States. doi:10.1063/1.2770701.
Curtiss, L. A., Redfern, P. C., Raghavachari, K., and Indiana Univ.. Mon . "Gaussian-4 theory using reduced perturbation orders.". United States. doi:10.1063/1.2770701.
@article{osti_953808,
title = {Gaussian-4 theory using reduced perturbation orders.},
author = {Curtiss, L. A. and Redfern, P. C. and Raghavachari, K. and Indiana Univ.},
abstractNote = {Two modifications of Gaussian-4 (G4) theory [L. A. Curtiss et al., J. Chem. Phys. 126, 084108 (2007)] are presented in which second- and third-order perturbation theories are used in place of fourth-order perturbation theory. These two new methods are referred to as G4(MP2) and G4(MP3), respectively. Both methods have been assessed on the G3/05 test set of accurate experimental data. The average absolute deviation from experiment for the 454 energies in this test set is 1.04 kcal/mol for G4(MP2) theory and 1.03 kcal/mol for G4(MP3) theory compared to 0.83 kcal/mol for G4 theory. G4(MP2) is slightly more accurate for enthalpies of formation than G4(MP3) (0.99 versus 1.04 kcal/mol), while G4(MP3) is more accurate for ionization potentials and electron affinities. Overall, the G4(MP2) method provides an accurate and economical method for thermochemical predictions. It has an overall accuracy for the G3/05 test set that is much better than G3(MP2) theory (1.04 versus 1.39 kcal/mol) and even better than G3 theory (1.04 versus 1.13 kcal/mol). In addition, G4(MP2) does better for challenging hypervalent systems such as H2SO4 and for nonhydrogen species than G3(MP2) theory.},
doi = {10.1063/1.2770701},
journal = {J. Chem. Phys.},
number = 2007,
volume = 127,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}
  • Two variations of Gaussian-2 (G2) theory are presented. In the first, referred to as G2 (MP2) theory, the basis-set-extension energy corrections are obtained at the 2nd order Moller--Plesset (MP2) level and in the second, referred to as G2(MP3) theory, they are obtained at the MP3 level. The methods are tested out on the set of 125 systems used for validation of G2 theory [J. Chem Phys. [bold 94], 7221 (1991)]. The average absolute deviation of the G2(MP2) and G2(MP3) theories from experiment are 1.58 and 1.52 kcal/mol, respectively, compared to 1.21 kcal/mol for G2 theory. The new methods provide significantmore » savings in computational time and disk storage.« less
  • A variation of Gaussian-3 (G3) theory is presented in which the basis set extensions are obtained at the second-order Mo/ller{endash}Plesset level. This method, referred to as G3(MP2) theory, is assessed on 299 energies from the G2/97 test set [J. Chem. Phys. {bold 109}, 42 (1998)]. The average absolute deviation from experiment of G3(MP2) theory for the 299 energies is 1.30 kcal/mol and for the subset of 148 neutral enthalpies it is 1.18 kcal/mol. This is a significant improvement over the related G2(MP2) theory [J. Chem. Phys. {bold 98}, 1293 (1993)], which has an average absolute deviation of 1.89 kcal/mol formore » all 299 energies and 2.03 kcal/mol for the 148 neutral enthalpies. The corresponding average absolute deviations for full G3 theory are 1.01 and 0.94 kcal/mol, respectively. The new method provides significant savings in computational time compared to G3 theory and, also, G2(MP2) theory.{copyright} {ital 1999 American Institute of Physics.}« less
  • A variation of Gaussian-3 (G3) theory is presented in which the basis set extensions are obtained at the second-order Moeller-Plesset level. This method, referred to as G3(MP2) theory, is assessed on 299 energies from the G2/97 test set [J. Chem. Phys. 109, 42 (1998)]. The average absolute deviation from experiment of G3(MP2) theory for the 299 energies is 1.30 kcal/mol and for the subset of 148 neutral enthalpies it is 1.18 kcal/mol. This is a significant improvement over the related G2(MP2) theory [J. Chem. Phys. 98, 1293 (1993)], which has an average absolute deviation of 1.89 kcal/mol for all 299more » energies and 2.03 kcal/mol for the 148 neutral enthalpies. The corresponding average absolute deviations for full G3 theory are 1.01 and 0.94 kcal/mol, respectively. The new method provides significant savings in computational time compared to G3 theory and, also, G2(MP2) theory.« less