Understanding Density-Driven Errors for Reaction Barrier Heights

Kaplan, Aaron D.; Shahi, Chandra; Bhetwal, Pradeep; Sah, Raj K.; Perdew, John P.

doi:10.1021/acs.jctc.2c00953

Understanding Density-Driven Errors for Reaction Barrier Heights

Journal Article · 03 January 2023 · Journal of Chemical Theory and Computation

DOI:https://doi.org/10.1021/acs.jctc.2c00953· OSTI ID:2420767

^[1]; Shahi, Chandra ^[2]; Bhetwal, Pradeep ^[2]; Sah, Raj K. ^[2]; ^[3]

Department of Physics, Temple University, Philadelphia, Pennsylvania19122, United States; OSTI
Department of Physics, Temple University, Philadelphia, Pennsylvania19122, United States
Department of Physics, Temple University, Philadelphia, Pennsylvania19122, United States; Department of Chemistry, Temple University, Philadelphia, Pennsylvania19122, United States

Not provided.

Research Organization:: Central Michigan Univ., Mount Pleasant, MI (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

DOE Contract Number:: SC0018331

OSTI ID:: 2420767

Journal Information:: Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 2 Vol. 19; ISSN 1549-9618

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

References (79)

Fractional charge perspective on the band gap in density-functional theory Cohen, Aron J.; Mori-Sánchez, Paula; Yang, Weitao Physical Review B, Vol. 77, Issue 11 https://doi.org/10.1103/PhysRevB.77.115123	journal	March 2008
Accurate and Numerically Efficient r ² SCAN Meta-Generalized Gradient Approximation Furness, James W.; Kaplan, Aaron D.; Ning, Jinliang The Journal of Physical Chemistry Letters, Vol. 11, Issue 19 https://doi.org/10.1021/acs.jpclett.0c02405	journal	September 2020
Density-Functional Theory for Fractional Particle Number: Derivative Discontinuities of the Energy Perdew, John P.; Parr, Robert G.; Levy, Mel Physical Review Letters, Vol. 49, Issue 23 https://doi.org/10.1103/PhysRevLett.49.1691	journal	December 1982
Density functional theory is straying from the path toward the exact functional Medvedev, Michael G.; Bushmarinov, Ivan S.; Sun, Jianwei Science, Vol. 355, Issue 6320 https://doi.org/10.1126/science.aah5975	journal	January 2017
Complex Orbitals, Multiple Local Minima, and Symmetry Breaking in Perdew–Zunger Self-Interaction Corrected Density Functional Theory Calculations Lehtola, Susi; Head-Gordon, Martin; Jónsson, Hannes Journal of Chemical Theory and Computation, Vol. 12, Issue 7 https://doi.org/10.1021/acs.jctc.6b00347	journal	June 2016
A look at the density functional theory zoo with the advanced GMTKN55 database for general main group thermochemistry, kinetics and noncovalent interactions Goerigk, Lars; Hansen, Andreas; Bauer, Christoph Physical Chemistry Chemical Physics, Vol. 19, Issue 48 https://doi.org/10.1039/C7CP04913G	journal	January 2017
Hartree–Fock orbitals significantly improve the reaction barrier heights predicted by semilocal density functionals Janesko, Benjamin G.; Scuseria, Gustavo E. The Journal of Chemical Physics, Vol. 128, Issue 24 https://doi.org/10.1063/1.2940738	journal	June 2008
Stretched or noded orbital densities and self-interaction correction in density functional theory Shahi, Chandra; Bhattarai, Puskar; Wagle, Kamal The Journal of Chemical Physics, Vol. 150, Issue 17 https://doi.org/10.1063/1.5087065	journal	May 2019
Generalized gradient approximation for the exchange-correlation hole of a many-electron system Perdew, John P.; Burke, Kieron; Wang, Yue Physical Review B, Vol. 54, Issue 23 https://doi.org/10.1103/PhysRevB.54.16533	journal	December 1996
Interpretation and Automatic Generation of Fermi‐Orbital Descriptors Schwalbe, Sebastian; Trepte, Kai; Fiedler, Lenz Journal of Computational Chemistry, Vol. 40, Issue 32 https://doi.org/10.1002/jcc.26062	journal	September 2019
Gaussian basis sets of quadruple zeta valence quality for atoms H–Kr Weigend, Florian; Furche, Filipp; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 119, Issue 24 https://doi.org/10.1063/1.1627293	journal	December 2003
How Good Is the Density-Corrected SCAN Functional for Neutral and Ionic Aqueous Systems, and What Is So Right about the Hartree–Fock Density? Dasgupta, Saswata; Shahi, Chandra; Bhetwal, Pradeep Journal of Chemical Theory and Computation, Vol. 18, Issue 8 https://doi.org/10.1021/acs.jctc.2c00313	journal	July 2022
A real-space model of nondynamical correlation Becke, Axel D. The Journal of Chemical Physics, Vol. 119, Issue 6 https://doi.org/10.1063/1.1589733	journal	August 2003
Complex Fermi–Löwdin orbital self-interaction correction Withanage, Kushantha P. K.; Jackson, Koblar A.; Pederson, Mark R. The Journal of Chemical Physics, Vol. 156, Issue 23 https://doi.org/10.1063/5.0091212	journal	June 2022
Can short-range hybrids describe long-range-dependent properties? Henderson, Thomas M.; Izmaylov, Artur F.; Scalmani, Giovanni The Journal of Chemical Physics, Vol. 131, Issue 4 https://doi.org/10.1063/1.3185673	journal	July 2009
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Weigend, Florian; Ahlrichs, Reinhart Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305 https://doi.org/10.1039/b508541a	journal	January 2005
Density-Corrected DFT Explained: Questions and Answers Song, Suhwan; Vuckovic, Stefan; Sim, Eunji Journal of Chemical Theory and Computation, Vol. 18, Issue 2 https://doi.org/10.1021/acs.jctc.1c01045	journal	January 2022
Results obtained with the correlation energy density functionals of becke and Lee, Yang and Parr Miehlich, Burkhard; Savin, Andreas; Stoll, Hermann Chemical Physics Letters, Vol. 157, Issue 3 https://doi.org/10.1016/0009-2614(89)87234-3	journal	May 1989
Comparison of coupled‐cluster results with a hybrid of Hartree–Fock and density functional theory Scuseria, Gustavo E. The Journal of Chemical Physics, Vol. 97, Issue 10 https://doi.org/10.1063/1.463977	journal	November 1992
Density functionals that are one- and two- are not always many-electron self-interaction-free, as shown for H2+, He2+, LiH+, and Ne2+ Ruzsinszky, Adrienn; Perdew, John P.; Csonka, Gábor I. The Journal of Chemical Physics, Vol. 126, Issue 10 https://doi.org/10.1063/1.2566637	journal	March 2007
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F. The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627 https://doi.org/10.1021/j100096a001	journal	November 1994
MN15-L: A New Local Exchange-Correlation Functional for Kohn–Sham Density Functional Theory with Broad Accuracy for Atoms, Molecules, and Solids Yu, Haoyu S.; He, Xiao; Truhlar, Donald G. Journal of Chemical Theory and Computation, Vol. 12, Issue 3 https://doi.org/10.1021/acs.jctc.5b01082	journal	February 2016
Rationale for mixing exact exchange with density functional approximations Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985 https://doi.org/10.1063/1.472933	journal	December 1996
Fractional spins and static correlation error in density functional theory Cohen, Aron J.; Mori-Sánchez, Paula; Yang, Weitao The Journal of Chemical Physics, Vol. 129, Issue 12 https://doi.org/10.1063/1.2987202	journal	September 2008
Efficient calculation of short-range Coulomb energies Adamson, Ross D.; Dombroski, Jeremy P.; Gill, Peter M. W. Journal of Computational Chemistry, Vol. 20, Issue 9 https://doi.org/10.1002/(SICI)1096-987X(19990715)20:9<921::AID-JCC3>3.0.CO;2-K	journal	July 1999
A long-range correction scheme for generalized-gradient-approximation exchange functionals Iikura, Hisayoshi; Tsuneda, Takao; Yanai, Takeshi The Journal of Chemical Physics, Vol. 115, Issue 8 https://doi.org/10.1063/1.1383587	journal	August 2001
Improving “difficult” reaction barriers with self-interaction corrected density functional theory Patchkovskii, Serguei; Ziegler, Tom The Journal of Chemical Physics, Vol. 116, Issue 18 https://doi.org/10.1063/1.1468640	journal	May 2002
Exact-exchange energy density in the gauge of a semilocal density-functional approximation Tao, Jianmin; Staroverov, Viktor N.; Scuseria, Gustavo E. Physical Review A, Vol. 77, Issue 1 https://doi.org/10.1103/PhysRevA.77.012509	journal	January 2008
A systematic comparison of molecular properties obtained using Hartree–Fock, a hybrid Hartree–Fock density‐functional‐theory, and coupled‐cluster methods Oliphant, Nevin; Bartlett, Rodney J. The Journal of Chemical Physics, Vol. 100, Issue 9 https://doi.org/10.1063/1.467064	journal	May 1994
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
A step in the direction of resolving the paradox of Perdew–Zunger self-interaction correction. II. Gauge consistency of the energy density at three levels of approximation Bhattarai, Puskar; Wagle, Kamal; Shahi, Chandra The Journal of Chemical Physics, Vol. 152, Issue 21 https://doi.org/10.1063/5.0010375	journal	June 2020
Localized orbital scaling correction for systematic elimination of delocalization error in density functional approximations Li, Chen; Zheng, Xiao; Su, Neil Qiang National Science Review, Vol. 5, Issue 2 https://doi.org/10.1093/nsr/nwx111	journal	September 2017
Optimization of Gaussian basis sets for density-functional calculations Porezag, Dirk; Pederson, Mark R. Physical Review A, Vol. 60, Issue 4 https://doi.org/10.1103/PhysRevA.60.2840	journal	October 1999
Libcint: An efficient general integral library for Gaussian basis functions Sun, Qiming Journal of Computational Chemistry, Vol. 36, Issue 22 https://doi.org/10.1002/jcc.23981	journal	June 2015
The Importance of Being Inconsistent Wasserman, Adam; Nafziger, Jonathan; Jiang, Kaili Annual Review of Physical Chemistry, Vol. 68, Issue 1 https://doi.org/10.1146/annurev-physchem-052516-044957	journal	May 2017
Exact results for the charge and spin densities, exchange-correlation potentials, and density-functional eigenvalues Almbladh, C. -O.; von Barth, U. Physical Review B, Vol. 31, Issue 6 https://doi.org/10.1103/PhysRevB.31.3231	journal	March 1985
Inverse Kohn–Sham Density Functional Theory: Progress and Challenges Shi, Yuming; Wasserman, Adam The Journal of Physical Chemistry Letters, Vol. 12, Issue 22 https://doi.org/10.1021/acs.jpclett.1c00752	journal	June 2021
Extending density functional theory with near chemical accuracy beyond pure water Song, Suhwan; Vuckovic, Stefan; Kim, Youngsam arXiv https://doi.org/10.48550/ARXIV.2207.04169	preprint	January 2022
Range separated hybrid density functional with long-range Hartree-Fock exchange applied to solids Gerber, Iann C.; Ángyán, János G.; Marsman, Martijn The Journal of Chemical Physics, Vol. 127, Issue 5 https://doi.org/10.1063/1.2759209	journal	August 2007
Tests of functionals for systems with fractional electron number Vydrov, Oleg A.; Scuseria, Gustavo E.; Perdew, John P. The Journal of Chemical Physics, Vol. 126, Issue 15 https://doi.org/10.1063/1.2723119	journal	April 2007
A step in the direction of resolving the paradox of Perdew-Zunger self-interaction correction Zope, Rajendra R.; Yamamoto, Yoh; Diaz, Carlos M. The Journal of Chemical Physics, Vol. 151, Issue 21 https://doi.org/10.1063/1.5129533	journal	December 2019
Fermi orbital derivatives in self-interaction corrected density functional theory: Applications to closed shell atoms Pederson, Mark R. The Journal of Chemical Physics, Vol. 142, Issue 6 https://doi.org/10.1063/1.4907592	journal	February 2015
Reducing density-driven error without exact exchange Janesko, Benjamin G. Physical Chemistry Chemical Physics, Vol. 19, Issue 6 https://doi.org/10.1039/C6CP08108H	journal	January 2017
Density Functional Analysis: The Theory of Density-Corrected DFT Vuckovic, Stefan; Song, Suhwan; Kozlowski, John Journal of Chemical Theory and Computation, Vol. 15, Issue 12 https://doi.org/10.1021/acs.jctc.9b00826	journal	November 2019
Assessment of a long-range corrected hybrid functional Vydrov, Oleg A.; Scuseria, Gustavo E. The Journal of Chemical Physics, Vol. 125, Issue 23 https://doi.org/10.1063/1.2409292	journal	December 2006
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Full self-consistency in the Fermi-orbital self-interaction correction Yang, Zeng-hui; Pederson, Mark R.; Perdew, John P. Physical Review A, Vol. 95, Issue 5 https://doi.org/10.1103/PhysRevA.95.052505	journal	May 2017
Convergence acceleration of iterative sequences. the case of scf iteration Pulay, Péter Chemical Physics Letters, Vol. 73, Issue 2 https://doi.org/10.1016/0009-2614(80)80396-4	journal	July 1980
Hellmann-Feynman, virial, and scaling requisites for the exact universal density functionals. Shape of the correlation potential and diamagnetic susceptibility for atoms Levy, Mel; Perdew, John P. Physical Review A, Vol. 32, Issue 4 https://doi.org/10.1103/PhysRevA.32.2010	journal	October 1985
Communication: Self-interaction correction with unitary invariance in density functional theory Pederson, Mark R.; Ruzsinszky, Adrienn; Perdew, John P. The Journal of Chemical Physics, Vol. 140, Issue 12 https://doi.org/10.1063/1.4869581	journal	March 2014
Benchmark Database of Barrier Heights for Heavy Atom Transfer, Nucleophilic Substitution, Association, and Unimolecular Reactions and Its Use to Test Theoretical Methods Zhao, Yan; González-García, Núria; Truhlar, Donald G. The Journal of Physical Chemistry A, Vol. 109, Issue 9 https://doi.org/10.1021/jp045141s	journal	March 2005
One - determinantal pure state versus ensemble Kohn-Sham solutions in the case of strong electron correlation: CH 2 and C 2 Schipper, P. R. T.; Gritsenko, O. V.; Baerends, E. J. Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 99, Issue 5 https://doi.org/10.1007/s002140050343	journal	September 1998
Fermi-Löwdin orbital self-interaction correction using the strongly constrained and appropriately normed meta-GGA functional Yamamoto, Yoh; Diaz, Carlos M.; Basurto, Luis The Journal of Chemical Physics, Vol. 151, Issue 15 https://doi.org/10.1063/1.5120532	journal	October 2019
Recent developments in the P y SCF program package Sun, Qiming; Zhang, Xing; Banerjee, Samragni The Journal of Chemical Physics, Vol. 153, Issue 2 https://doi.org/10.1063/5.0006074	journal	July 2020
New Basis Set Exchange: An Open, Up-to-Date Resource for the Molecular Sciences Community Pritchard, Benjamin P.; Altarawy, Doaa; Didier, Brett Journal of Chemical Information and Modeling, Vol. 59, Issue 11 https://doi.org/10.1021/acs.jcim.9b00725	journal	October 2019
Pushing the frontiers of density functionals by solving the fractional electron problem Kirkpatrick, James; McMorrow, Brendan; Turban, David H. P. Science, Vol. 374, Issue 6573 https://doi.org/10.1126/science.abj6511	journal	December 2021
A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions Zhao, Yan; Truhlar, Donald G. The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101 https://doi.org/10.1063/1.2370993	journal	November 2006
What Types of Chemical Problems Benefit from Density-Corrected DFT? A Probe Using an Extensive and Chemically Diverse Test Suite Santra, Golokesh; Martin, Jan M. L. Journal of Chemical Theory and Computation, Vol. 17, Issue 3 https://doi.org/10.1021/acs.jctc.0c01055	journal	February 2021
Why semilocal functionals work: Accuracy of the on-top pair density and importance of system averaging Burke, Kieron; Perdew, John P.; Ernzerhof, Matthias The Journal of Chemical Physics, Vol. 109, Issue 10 https://doi.org/10.1063/1.476976	journal	September 1998
Strongly Constrained and Appropriately Normed Semilocal Density Functional Sun, Jianwei; Ruzsinszky, Adrienn; Perdew, John P. Physical Review Letters, Vol. 115, Issue 3 https://doi.org/10.1103/PhysRevLett.115.036402	journal	July 2015
Elevating density functional theory to chemical accuracy for water simulations through a density-corrected many-body formalism Dasgupta, Saswata; Lambros, Eleftherios; Perdew, John P. Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-26618-9	journal	November 2021
Density-functional exchange-energy approximation with correct asymptotic behavior Becke, A. D. Physical Review A, Vol. 38, Issue 6 https://doi.org/10.1103/PhysRevA.38.3098	journal	September 1988
Quantifying Density Errors in DFT Sim, Eunji; Song, Suhwan; Burke, Kieron The Journal of Physical Chemistry Letters, Vol. 9, Issue 22 https://doi.org/10.1021/acs.jpclett.8b02855	journal	October 2018
Accurate and simple analytic representation of the electron-gas correlation energy Perdew, John P.; Wang, Yue Physical Review B, Vol. 45, Issue 23, p. 13244-13249 https://doi.org/10.1103/PhysRevB.45.13244	journal	June 1992
Study of self-interaction-errors in barrier heights using locally scaled and Perdew–Zunger self-interaction methods Mishra, Prakash; Yamamoto, Yoh; Johnson, J. Karl The Journal of Chemical Physics, Vol. 156, Issue 1 https://doi.org/10.1063/5.0070893	journal	January 2022
P y SCF: the Python-based simulations of chemistry framework : The PySCF program Sun, Qiming; Berkelbach, Timothy C.; Blunt, Nick S. Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 1 https://doi.org/10.1002/wcms.1340	journal	September 2017
Data for "Understanding density driven errors via reaction barrier heights" Kaplan, Aaron D.; Shahi, Chandra; Bhetwal, Pradeep Zenodo https://doi.org/10.5281/zenodo.7438920	dataset	January 2022
PyFLOSIC: Python-based Fermi–Löwdin orbital self-interaction correction Schwalbe, Sebastian; Fiedler, Lenz; Kraus, Jakob The Journal of Chemical Physics, Vol. 153, Issue 8 https://doi.org/10.1063/5.0012519	journal	August 2020
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Combining long-range configuration interaction with short-range density functionals Leininger, Thierry; Stoll, Hermann; Werner, Hans-Joachim Chemical Physics Letters, Vol. 275, Issue 3-4 https://doi.org/10.1016/S0009-2614(97)00758-6	journal	August 1997
Seven Useful Questions in Density Functional Theory Crisostomo, Steven; Pederson, Ryan; Kozlowski, John arXiv https://doi.org/10.48550/ARXIV.2207.05794	text	January 2022
Understanding and Reducing Errors in Density Functional Calculations Kim, Min-Cheol; Sim, Eunji; Burke, Kieron Physical Review Letters, Vol. 111, Issue 7 https://doi.org/10.1103/PhysRevLett.111.073003	journal	August 2013
Increasing the applicability of DFT I: Non-variational correlation corrections from Hartree–Fock DFT for predicting transition states Verma, Prakash; Perera, Ajith; Bartlett, Rodney J. Chemical Physics Letters, Vol. 524 https://doi.org/10.1016/j.cplett.2011.12.017	journal	February 2012
Exchange and correlation in density-functional theory Sham, L. J. Physical Review B, Vol. 32, Issue 6 https://doi.org/10.1103/PhysRevB.32.3876	journal	September 1985
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen Dunning, Thom H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456153	journal	January 1989
What do the Kohn-Sham Orbital Energies Mean? How do Atoms Dissociate? Perdew, John P. https://doi.org/10.1007/978-1-4757-0818-9_10	book
Self-interaction correction to density-functional approximations for many-electron systems Perdew, J. P.; Zunger, Alex Physical Review B, Vol. 23, Issue 10, p. 5048-5079 https://doi.org/10.1103/PhysRevB.23.5048	journal	May 1981
Measuring Density-Driven Errors Using Kohn–Sham Inversion Nam, Seungsoo; Song, Suhwan; Sim, Eunji Journal of Chemical Theory and Computation, Vol. 16, Issue 8 https://doi.org/10.1021/acs.jctc.0c00391	journal	July 2020

Similar Records

The rise and fall of stretched bond errors: Extending the analysis of Perdew–Zunger self-interaction corrections of reaction barrier heights beyond the LSDA

Journal Article · 2024 · Journal of Chemical Physics · OSTI ID:2328493

How Do Self-Interaction Errors Associated with Stretched Bonds Affect Barrier Height Predictions?

Journal Article · 2023 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory · OSTI ID:1962956

Related Subjects

Chemistry
Physics

Understanding Density-Driven Errors for Reaction Barrier Heights

Citation Formats

References (79)

Similar Records

Related Subjects