An examination of intrinsic errors in electronic structure methods using the Environmental Molecular Sciences Laboratory computational results database and the Gaussian-2 set
Abstract
We present that the Gaussian-2 (G2) collection of atoms and molecules has been studied with Hartree–Fock and correlated levels of theory, ranging from second-order perturbation theory to coupled cluster theory with noniterative inclusion of triple excitations. By exploiting the systematic convergence properties of the correlation consistent family of basis sets, complete basis set limits were estimated for a large number of the G2 energetic properties. Deviations with respect to experimentally derived energy differences corresponding to rigid molecules were obtained for 15 basis set/method combinations, as well as the estimated complete basis set limit. The latter values are necessary for establishing the intrinsic error for each method. In order to perform this analysis, the information generated in the present study was combined with the results of many previous benchmark studies in an electronic database, where it is available for use by other software tools. Lastly, such tools can assist users of electronic structure codes in making appropriate basis set and method choices that will increase the likelihood of achieving their accuracy goals without wasteful expenditures of computer resources.
- Authors:
-
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Publication Date:
- Research Org.:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1491721
- Report Number(s):
- PNNL-SA-29230
Journal ID: ISSN 0021-9606
- Grant/Contract Number:
- AC05-76RL01830
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 108; Journal Issue: 1; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Feller, David, and Peterson, Kirk A. An examination of intrinsic errors in electronic structure methods using the Environmental Molecular Sciences Laboratory computational results database and the Gaussian-2 set. United States: N. p., 1998.
Web. doi:10.1063/1.475370.
Feller, David, & Peterson, Kirk A. An examination of intrinsic errors in electronic structure methods using the Environmental Molecular Sciences Laboratory computational results database and the Gaussian-2 set. United States. https://doi.org/10.1063/1.475370
Feller, David, and Peterson, Kirk A. Thu .
"An examination of intrinsic errors in electronic structure methods using the Environmental Molecular Sciences Laboratory computational results database and the Gaussian-2 set". United States. https://doi.org/10.1063/1.475370. https://www.osti.gov/servlets/purl/1491721.
@article{osti_1491721,
title = {An examination of intrinsic errors in electronic structure methods using the Environmental Molecular Sciences Laboratory computational results database and the Gaussian-2 set},
author = {Feller, David and Peterson, Kirk A.},
abstractNote = {We present that the Gaussian-2 (G2) collection of atoms and molecules has been studied with Hartree–Fock and correlated levels of theory, ranging from second-order perturbation theory to coupled cluster theory with noniterative inclusion of triple excitations. By exploiting the systematic convergence properties of the correlation consistent family of basis sets, complete basis set limits were estimated for a large number of the G2 energetic properties. Deviations with respect to experimentally derived energy differences corresponding to rigid molecules were obtained for 15 basis set/method combinations, as well as the estimated complete basis set limit. The latter values are necessary for establishing the intrinsic error for each method. In order to perform this analysis, the information generated in the present study was combined with the results of many previous benchmark studies in an electronic database, where it is available for use by other software tools. Lastly, such tools can assist users of electronic structure codes in making appropriate basis set and method choices that will increase the likelihood of achieving their accuracy goals without wasteful expenditures of computer resources.},
doi = {10.1063/1.475370},
journal = {Journal of Chemical Physics},
number = 1,
volume = 108,
place = {United States},
year = {Thu Jan 01 00:00:00 EST 1998},
month = {Thu Jan 01 00:00:00 EST 1998}
}
Web of Science
Figures / Tables:
Works referenced in this record:
Gaussian‐2 theory: Use of higher level correlation methods, quadratic configuration interaction geometries, and second‐order Mo/ller–Plesset zero‐point energies
journal, September 1995
- Curtiss, Larry A.; Raghavachari, Krishnan; Pople, John A.
- The Journal of Chemical Physics, Vol. 103, Issue 10
Properties of the monofluorides of nitrogen, silicon, phosphorus, and sulfur from a molecular orbital study
journal, October 1973
- O'Hare, P. A. G.
- The Journal of Chemical Physics, Vol. 59, Issue 7
Limiting values for Mo/ller–Plesset second‐order correlation energies of polyatomic systems: A benchmark study on Ne, HF, H 2 O, N 2 , and He...He
journal, April 1995
- Klopper, Wim
- The Journal of Chemical Physics, Vol. 102, Issue 15
A complete basis set model chemistry. V. Extensions to six or more heavy atoms
journal, February 1996
- Ochterski, Joseph W.; Petersson, G. A.; Montgomery, J. A.
- The Journal of Chemical Physics, Vol. 104, Issue 7
Benchmark calculations with correlated molecular wave functions. X. Comparison with “exact” MP2 calculations on Ne, HF, H2O, and N2
journal, June 1997
- Wilson, Angela K.; Dunning, Jr., Thom H.
- The Journal of Chemical Physics, Vol. 106, Issue 21
A modification of the Gaussian‐2 approach using density functional theory
journal, August 1995
- Bauschlicher, Charles W.; Partridge, Harry
- The Journal of Chemical Physics, Vol. 103, Issue 5
Ab initio total atomization energies of small molecules — towards the basis set limit
journal, September 1996
- Martin, Jan M. L.
- Chemical Physics Letters, Vol. 259, Issue 5-6
A lower limit for ΔHf0(NF) and the excitation transfer reactions of N2(A 3Σu+) with NCO(X̃ 2Πi) and NF(X 3Σ−)
journal, December 1988
- Du, Kang-Yan; Setser, D. W.
- Chemical Physics Letters, Vol. 153, Issue 5
A systematic study of molecular vibrational anharmonicity and vibration—rotation interaction by self-consistent-field higher-derivative methods. Asymmetric top molecules
journal, July 1988
- Clabo, D. Allen; Allen, Wesley D.; Remington, Richard B.
- Chemical Physics, Vol. 123, Issue 2
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989
- Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 90, Issue 2
Gaussian‐1 theory of molecular energies for second‐row compounds
journal, August 1990
- Curtiss, Larry A.; Jones, Christopher; Trucks, Gary W.
- The Journal of Chemical Physics, Vol. 93, Issue 4
Theoretical characterization of negative ions. Calculation of the electron affinities of carbon, oxygen, and fluorine
journal, June 1982
- Botch, Beatrice H.; Dunning, Thom. H.
- The Journal of Chemical Physics, Vol. 76, Issue 12
The electron affinity of oxygen: A systematic configuration interaction approach
journal, January 1989
- Feller, David; Davidson, Ernest R.
- The Journal of Chemical Physics, Vol. 90, Issue 2
The potential surface and stretching frequencies of X ̃ 3 B 1 methylene (CH 2 ) determined from experiment using the Morse oscillator‐rigid bender internal dynamics Hamiltonian
journal, August 1988
- Jensen, Per; Bunker, P. R.
- The Journal of Chemical Physics, Vol. 89, Issue 3
The use of systematic sequences of wave functions for estimating the complete basis set, full configuration interaction limit in water
journal, May 1993
- Feller, David
- The Journal of Chemical Physics, Vol. 98, Issue 9
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992
- Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J.
- The Journal of Chemical Physics, Vol. 96, Issue 9
On the performance of large Gaussian basis sets for the computation of total atomization energies
journal, October 1992
- Martin, J. M. L.
- The Journal of Chemical Physics, Vol. 97, Issue 7
An efficient internally contracted multiconfiguration–reference configuration interaction method
journal, November 1988
- Werner, Hans‐Joachim; Knowles, Peter J.
- The Journal of Chemical Physics, Vol. 89, Issue 9
Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon
journal, January 1993
- Woon, David E.; Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 98, Issue 2
A theoretical study of the electron affinity of methylene
journal, September 1989
- Noro, Takeshi; Yoshimine, Megumu
- The Journal of Chemical Physics, Vol. 91, Issue 5
First row benchmark tests of the parametrized configuration interaction with parameter X (PCI‐ X ) scheme
journal, April 1995
- Siegbahn, Per E. M.; Svensson, Mats; Boussard, Per J. E.
- The Journal of Chemical Physics, Vol. 102, Issue 13
Gaussian basis sets for use in correlated molecular calculations. VI. Sextuple zeta correlation consistent basis sets for boron through neon
journal, December 1996
- Wilson, Angela K.; van Mourik, Tanja; Dunning, Thom H.
- Journal of Molecular Structure: THEOCHEM, Vol. 388
Benchmark calculations with correlated molecular wave functions. III. Configuration interaction calculations on first row homonuclear diatomics
journal, December 1993
- Peterson, Kirk A.; Kendall, Rick A.; Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 99, Issue 12
Hydrogen fluoride: a critical comparison of theoretical and experimental results
journal, July 1997
- Feller, David; Peterson, Kirk A.
- Journal of Molecular Structure: THEOCHEM, Vol. 400
The atomization energy and proton affinity of NH3. An ab initio calibration study
journal, August 1996
- Martin, Jan M. L.; Lee, Timothy J.
- Chemical Physics Letters, Vol. 258, Issue 1-2
A systematic study of molecular vibrational anharmonicity and vibration-rotation interaction by self-consistent-field higher-derivative methods. Linear polyatomic molecules
journal, September 1990
- Allen, Wesley D.; Yamaguchi, Yukio; Császár, Attila G.
- Chemical Physics, Vol. 145, Issue 3
Configuration interaction calculations on the nitrogen molecule
journal, January 1974
- Langhoff, Stephen R.; Davidson, Ernest R.
- International Journal of Quantum Chemistry, Vol. 8, Issue 1
How large is the effect of 1 s correlation on the D e , ω e , and r e of N 2 ?
journal, March 1994
- Bauschlicher, Charles W.; Partridge, Harry
- The Journal of Chemical Physics, Vol. 100, Issue 6
Benchmark calculations with correlated molecular wave functions. I. Multireference configuration interaction calculations for the second row diatomic hydrides
journal, August 1993
- Woon, David E.; Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 99, Issue 3
Gaussian basis sets for use in correlated molecular calculations. IV. Calculation of static electrical response properties
journal, February 1994
- Woon, David E.; Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 100, Issue 4
Benchmark calculations with correlated molecular wave functions. II. Configuration interaction calculations on first row diatomic hydrides
journal, August 1993
- Peterson, Kirk A.; Kendall, Rick A.; Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 99, Issue 3
Anharmonic potential functions of polyatomic molecules
journal, July 1967
- Plíva, J.; Špirko, V.; Papoušek, D.
- Journal of Molecular Spectroscopy, Vol. 23, Issue 3
On the effect of core correlation on the geometry and harmonic frequencies of small polyatomic molecules
journal, August 1995
- Martin, Jan M. L.
- Chemical Physics Letters, Vol. 242, Issue 3
Benchmark calculations with correlated molecular wave functions. VI. Second row A 2 and first row/second row AB diatomic molecules
journal, November 1994
- Woon, David E.; Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 101, Issue 10
Application of systematic sequences of wave functions to the water dimer
journal, April 1992
- Feller, David
- The Journal of Chemical Physics, Vol. 96, Issue 8
Concerning zero‐point vibrational energy corrections to electronic energies
journal, October 1991
- Grev, Roger S.; Janssen, Curtis L.; Schaefer, Henry F.
- The Journal of Chemical Physics, Vol. 95, Issue 7
Gaussian basis sets for use in correlated molecular calculations. V. Core‐valence basis sets for boron through neon
journal, September 1995
- Woon, David E.; Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 103, Issue 11
The total atomization energy and heat of formation of HCN(g)
journal, September 1996
- Martin, Jan M. L.
- Chemical Physics Letters, Vol. 259, Issue 5-6
Benchmark calculations with correlated molecular wave functions. VII. Binding energy and structure of the HF dimer
journal, February 1995
- Peterson, Kirk A.; Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 102, Issue 5
Quantum‐Chemical Study of Some Pnicogen Monofluorides
journal, June 1971
- O'Hare, P. A. G.; Wahl, Arnold C.
- The Journal of Chemical Physics, Vol. 54, Issue 11
The dissociation energies of NF(X 3Σ−) and NCl(X 3Σ−)
journal, February 1997
- Xantheas, Sotiris S.; Dunning, Thom H.; Mavridis, Aristides
- The Journal of Chemical Physics, Vol. 106, Issue 8
Gaussian‐2 theory for molecular energies of first‐ and second‐row compounds
journal, June 1991
- Curtiss, Larry A.; Raghavachari, Krishnan; Trucks, Gary W.
- The Journal of Chemical Physics, Vol. 94, Issue 11
Assessment of Gaussian-2 and density functional theories for the computation of enthalpies of formation
journal, January 1997
- Curtiss, Larry A.; Raghavachari, Krishnan; Redfern, Paul C.
- The Journal of Chemical Physics, Vol. 106, Issue 3
A study of vibrational anharmonicity, fermi resonance interactions, and local mode behavior in CH3Cl
journal, March 1990
- Duncan, J. L.; Law, M. M.
- Journal of Molecular Spectroscopy, Vol. 140, Issue 1
The anharmonic force field and equilibrium structure of methane
journal, June 1979
- Gray, D. L.; Robiette, A. G.
- Molecular Physics, Vol. 37, Issue 6
The CO molecule: the role of basis set and correlation treatment in the calculation of molecular properties
journal, July 1997
- Peterson, Kirk A.; Dunning, Thom H.
- Journal of Molecular Structure: THEOCHEM, Vol. 400
The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors
journal, October 1970
- Boys, S.F.; Bernardi, F.
- Molecular Physics, Vol. 19, Issue 4, p. 553-566
Accurate numerical orbital MBPT/CC study of the electron affinity of fluorine and the dissociation energy of hydrogen fluoride
journal, June 1986
- Adamowicz, Ludwik; Bartlett, Rodney J.
- The Journal of Chemical Physics, Vol. 84, Issue 12
The dissociation energy of CN and C 2
journal, September 1994
- Pradhan, Atul D.; Partridge, Harry; Bauschlicher, Charles W.
- The Journal of Chemical Physics, Vol. 101, Issue 5
A complete basis set model chemistry. IV. An improved atomic pair natural orbital method
journal, October 1994
- Montgomery, J. A.; Ochterski, J. W.; Petersson, G. A.
- The Journal of Chemical Physics, Vol. 101, Issue 7
Configuration-interaction study of atoms. II. Electron affinities of B, C, N, O, and F
journal, January 1974
- Sasaki, F.; Yoshimine, M.
- Physical Review A, Vol. 9, Issue 1
On the performance of correlation consistent basis sets for the calculation of total atomization energies, geometries, and harmonic frequencies
journal, June 1994
- Martin, Jan M. L.
- The Journal of Chemical Physics, Vol. 100, Issue 11
Works referencing / citing this record:
A Critical Assessment of Coupled Cluster Method in Quantum Chemistry
book, January 1999
- Paldus, Josef; Li, Xiangzhu; Prigogine, I.
- Advances in Chemical Physics: Prigogine/Advances
Ab Initio Study on the Mechanism of the Atmospheric Reaction OH+O3→HO2+O2
journal, August 2003
- Peiró-García, Julio; Nebot-Gil, Ignacio
- ChemPhysChem, Vol. 4, Issue 8
Local aromaticity mapping in the vicinity of planar and nonplanar molecules
journal, June 2019
- Kupka, Teobald; Gajda, Łukasz; Stobiński, Leszek
- Magnetic Resonance in Chemistry, Vol. 57, Issue 7
Ab Initio Thermochemistry Beyond Chemical Accuracy for First-and Second-Row Compounds
book, January 1999
- Martin, Jan M. L.; Minas da Piedade, M. E.
- Energetics of Stable Molecules and Reactive Intermediates, p. 373-415
Discovering chemistry with an ab initio nanoreactor
journal, November 2014
- Wang, Lee-Ping; Titov, Alexey; McGibbon, Robert
- Nature Chemistry, Vol. 6, Issue 12
Full configuration interaction benchmarking of coupled-cluster models for the lowest singlet energy surfaces of N2
journal, October 2000
- Larsen, Helena; Olsen, Jeppe; Jørgensen, Poul
- The Journal of Chemical Physics, Vol. 113, Issue 16
Approximating the basis set dependence of coupled cluster calculations: Evaluation of perturbation theory approximations for stable molecules
journal, November 2000
- Dunning, Thom H.; Peterson, Kirk A.
- The Journal of Chemical Physics, Vol. 113, Issue 18
Parallel Douglas–Kroll energy and gradients in NWChem: Estimating scalar relativistic effects using Douglas–Kroll contracted basis sets
journal, January 2001
- de Jong, W. A.; Harrison, R. J.; Dixon, D. A.
- The Journal of Chemical Physics, Vol. 114, Issue 1
The accurate determination of molecular equilibrium structures
journal, April 2001
- Bak, Keld L.; Gauss, Jürgen; Jørgensen, Poul
- The Journal of Chemical Physics, Vol. 114, Issue 15
Explicitly correlated second-order Møller–Plesset methods with auxiliary basis sets
journal, April 2002
- Klopper, Wim; Samson, Claire C. M.
- The Journal of Chemical Physics, Vol. 116, Issue 15
The correlation consistent composite approach (cc CA ): An alternative to the Gaussian-n methods
journal, March 2006
- DeYonker, Nathan J.; Cundari, Thomas R.; Wilson, Angela K.
- The Journal of Chemical Physics, Vol. 124, Issue 11
Gaussian-4 theory
journal, February 2007
- Curtiss, Larry A.; Redfern, Paul C.; Raghavachari, Krishnan
- The Journal of Chemical Physics, Vol. 126, Issue 8
A survey of factors contributing to accurate theoretical predictions of atomization energies and molecular structures
journal, November 2008
- Feller, David; Peterson, Kirk A.; Dixon, David A.
- The Journal of Chemical Physics, Vol. 129, Issue 20
Approaching chemical accuracy using full configuration-interaction quantum Monte Carlo: A study of ionization potentials
journal, May 2010
- Booth, George H.; Alavi, Ali
- The Journal of Chemical Physics, Vol. 132, Issue 17
Calibration study of the CCSD(T)-F12a/b methods for C2 and small hydrocarbons
journal, November 2010
- Feller, David; Peterson, Kirk A.; Hill, J. Grant
- The Journal of Chemical Physics, Vol. 133, Issue 18
On the effectiveness of CCSD(T) complete basis set extrapolations for atomization energies
journal, July 2011
- Feller, David; Peterson, Kirk A.; Grant Hill, J.
- The Journal of Chemical Physics, Vol. 135, Issue 4
Towards standard methods for benchmark quality ab initio thermochemistry—W1 and W2 theory
journal, August 1999
- Martin, Jan M. L.; de Oliveira, Glênisson
- The Journal of Chemical Physics, Vol. 111, Issue 5
Infinite basis limits in electronic structure theory
journal, August 1999
- Fast, Patton L.; Sánchez, Marı́a L.; Truhlar, Donald G.
- The Journal of Chemical Physics, Vol. 111, Issue 7
Assessment of Gaussian-3 and density functional theories for a larger experimental test set
journal, May 2000
- Curtiss, Larry A.; Raghavachari, Krishnan; Redfern, Paul C.
- The Journal of Chemical Physics, Vol. 112, Issue 17
Is Mo/ller–Plesset perturbation theory a convergent ab initio method?
journal, June 2000
- Leininger, Matthew L.; Allen, Wesley D.; Schaefer, Henry F.
- The Journal of Chemical Physics, Vol. 112, Issue 21
Basis set convergence of CCSD(T) equilibrium geometries using a large and diverse set of molecular structures
journal, September 2016
- Spackman, Peter R.; Jayatilaka, Dylan; Karton, Amir
- The Journal of Chemical Physics, Vol. 145, Issue 10
Estimating the intrinsic limit of the Feller-Peterson-Dixon composite approach when applied to adiabatic ionization potentials in atoms and small molecules
journal, July 2017
- Feller, David
- The Journal of Chemical Physics, Vol. 147, Issue 3
Quantitative quantum chemistry
journal, August 2008
- Helgaker, Trygve; Klopper, Wim; Tew, David P.
- Molecular Physics, Vol. 106, Issue 16-18
Resolution-of-identity approach to Hartree–Fock, hybrid density functionals, RPA, MP2 and GW with numeric atom-centered orbital basis functions
journal, May 2012
- Ren, Xinguo; Rinke, Patrick; Blum, Volker
- New Journal of Physics, Vol. 14, Issue 5
Phaseless auxiliary-field quantum Monte Carlo calculations with plane waves and pseudopotentials: Applications to atoms and molecules
journal, June 2007
- Suewattana, Malliga; Purwanto, Wirawan; Zhang, Shiwei
- Physical Review B, Vol. 75, Issue 24
Renormalized second-order perturbation theory for the electron correlation energy: Concept, implementation, and benchmarks
journal, July 2013
- Ren, Xinguo; Rinke, Patrick; Scuseria, Gustavo E.
- Physical Review B, Vol. 88, Issue 3
Calculations of hydrogenation enthalpies of hydrocarbons by M06-2X/CBS extrapolated level in the gas phase
journal, May 2020
- Khairbek, Aa; Badawi, M. Abd Al-Hakim
- Journal of Chemical Research
Phaseless auxiliary-field quantum Monte Carlo calculations with planewaves and pseudopotentials--applications to atoms and molecules
text, January 2007
- Suewattana, Malliga; Purwanto, Wirawan; Zhang, Shiwei
- arXiv
Insights Into the Origin of Life: Did It Begin from HCN and H 2 O?
journal, August 2019
- Das, Tamal; Ghule, Siddharth; Vanka, Kumar
- ACS Central Science, Vol. 5, Issue 9
Figures / Tables found in this record: