Can Kohn–Sham density functional theory predict accurate charge distributions for both single-reference and multi-reference molecules?
Abstract
Dipole moments are the first moment of electron density and are fundamental quantities that are often available from experiments. An exchange–correlation functional that leads to an accurate representation of the charge distribution of a molecule should accurately predict the dipole moments of the molecule. It is well known that Kohn–Sham density functional theory (DFT) is more accurate for the energetics of single-reference systems than for the energetics of multi-reference ones, but there has been less study of charge distributions. Here, in this work, we benchmark 48 density functionals chosen with various combinations of ingredients, against accurate experimental data for dipole moments of 78 molecules, in particular 55 single-reference molecules and 23 multi-reference ones. We chose both organic and inorganic molecules, and within the category of inorganic molecules there are both main-group and transition-metal-containing molecules, with some of them being multi-reference. As one would expect, the multi-reference molecules are not as well described by single-reference DFT, and the functionals tested in this work do show larger mean unsigned errors (MUEs) for the 23 multi-reference molecules than the single-reference ones. Five of the 78 molecules have relatively large experimental error bars and were therefore not included in calculating the overall MUEs. Formore »
- Authors:
-
- Univ. of Minnesota, Minneapolis, MN (United States)
- Publication Date:
- Research Org.:
- Univ. of Minnesota, Minneapolis, MN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
- OSTI Identifier:
- 2311160
- Grant/Contract Number:
- SC0008688; FG02-12ER16362
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 19; Journal Issue: 20; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Verma, Pragya, and Truhlar, Donald G. Can Kohn–Sham density functional theory predict accurate charge distributions for both single-reference and multi-reference molecules?. United States: N. p., 2017.
Web. doi:10.1039/c7cp01576c.
Verma, Pragya, & Truhlar, Donald G. Can Kohn–Sham density functional theory predict accurate charge distributions for both single-reference and multi-reference molecules?. United States. https://doi.org/10.1039/c7cp01576c
Verma, Pragya, and Truhlar, Donald G. Mon .
"Can Kohn–Sham density functional theory predict accurate charge distributions for both single-reference and multi-reference molecules?". United States. https://doi.org/10.1039/c7cp01576c. https://www.osti.gov/servlets/purl/2311160.
@article{osti_2311160,
title = {Can Kohn–Sham density functional theory predict accurate charge distributions for both single-reference and multi-reference molecules?},
author = {Verma, Pragya and Truhlar, Donald G.},
abstractNote = {Dipole moments are the first moment of electron density and are fundamental quantities that are often available from experiments. An exchange–correlation functional that leads to an accurate representation of the charge distribution of a molecule should accurately predict the dipole moments of the molecule. It is well known that Kohn–Sham density functional theory (DFT) is more accurate for the energetics of single-reference systems than for the energetics of multi-reference ones, but there has been less study of charge distributions. Here, in this work, we benchmark 48 density functionals chosen with various combinations of ingredients, against accurate experimental data for dipole moments of 78 molecules, in particular 55 single-reference molecules and 23 multi-reference ones. We chose both organic and inorganic molecules, and within the category of inorganic molecules there are both main-group and transition-metal-containing molecules, with some of them being multi-reference. As one would expect, the multi-reference molecules are not as well described by single-reference DFT, and the functionals tested in this work do show larger mean unsigned errors (MUEs) for the 23 multi-reference molecules than the single-reference ones. Five of the 78 molecules have relatively large experimental error bars and were therefore not included in calculating the overall MUEs. For the 73 molecules not excluded, we find that three of the hybrid functionals, B97-1, PBE0, and TPSSh (each with less than or equal to 25% Hartree–Fock (HF) exchange), the range-separated hybrid functional, HSE06 (with HF exchange decreasing from 25% to 0 as interelectronic distance increases), and the hybrid functional, PW6B95 (with 28% HF exchange) are the best performing functionals with each yielding an MUE of 0.18 D. Perhaps the most significant finding of this study is that there exists great similarity among the success rate of various functionals in predicting dipole moments. In particular, of 39 functionals designed as general-purpose functionals and that do not have a global value of 100% HF exchange, the average MUE is 0.23 D, with a standard deviation of only 0.04 D. Among gradient approximations, which are especially interesting because of their speed and portability, the best overall performance is by PBE, HCTH/407, OLYP, OreLYP, and GAM, each with MUE of 0.22 D.},
doi = {10.1039/c7cp01576c},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 20,
volume = 19,
place = {United States},
year = {Mon Apr 24 00:00:00 EDT 2017},
month = {Mon Apr 24 00:00:00 EDT 2017}
}
Web of Science
Works referenced in this record:
Density functional theory in surface chemistry and catalysis
journal, January 2011
- Norskov, J. K.; Abild-Pedersen, F.; Studt, F.
- Proceedings of the National Academy of Sciences, Vol. 108, Issue 3
Challenges for Density Functional Theory
journal, December 2011
- Cohen, Aron J.; Mori-Sánchez, Paula; Yang, Weitao
- Chemical Reviews, Vol. 112, Issue 1
Consistent descriptions of metal–ligand bonds and spin-crossover in inorganic chemistry
journal, January 2013
- Kepp, Kasper P.
- Coordination Chemistry Reviews, Vol. 257, Issue 1
Perspective: Kohn-Sham density functional theory descending a staircase
journal, October 2016
- Yu, Haoyu S.; Li, Shaohong L.; Truhlar, Donald G.
- The Journal of Chemical Physics, Vol. 145, Issue 13
Electronic Structures of Molecules XI. Electroaffinity, Molecular Orbitals and Dipole Moments
journal, September 1935
- Mulliken, Robert S.
- The Journal of Chemical Physics, Vol. 3, Issue 9
Bonded-atom fragments for describing molecular charge densities
journal, January 1977
- Hirshfeld, F. L.
- Theoretica Chimica Acta, Vol. 44, Issue 2
Comparison of the Hartree-Fock, M�ller-Plesset, and Hartree-Fock-Slater method with respect to electrostatic properties of small molecules: Effects of electron correlation
journal, October 1993
- Velders, Guus J. M.; Feil, Dirk
- Theoretica Chimica Acta, Vol. 86, Issue 5
Charge Model 5: An Extension of Hirshfeld Population Analysis for the Accurate Description of Molecular Interactions in Gaseous and Condensed Phases
journal, February 2012
- Marenich, Aleksandr V.; Jerome, Steven V.; Cramer, Christopher J.
- Journal of Chemical Theory and Computation, Vol. 8, Issue 2, p. 527-541
Performance of density functionals for first row transition metal systems
journal, January 2007
- Jensen, Kasper P.; Roos, Björn O.; Ryde, Ulf
- The Journal of Chemical Physics, Vol. 126, Issue 1
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005
- Weigend, Florian; Ahlrichs, Reinhart
- Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
Density Functionals for Inorganometallic and Organometallic Chemistry
journal, December 2005
- Schultz, Nathan E.; Zhao, Yan; Truhlar, Donald G.
- The Journal of Physical Chemistry A, Vol. 109, Issue 49
A simple DFT-based diagnostic for nondynamical correlation
journal, December 2012
- Fogueri, Uma R.; Kozuch, Sebastian; Karton, Amir
- Theoretical Chemistry Accounts, Vol. 132, Issue 1
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988
- Lee, Chengteh; Yang, Weitao; Parr, Robert G.
- Physical Review B, Vol. 37, Issue 2
Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988
- Becke, A. D.
- Physical Review A, Vol. 38, Issue 6
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
A new parametrization of exchange–correlation generalized gradient approximation functionals
journal, April 2001
- Boese, A. Daniel; Handy, Nicholas C.
- The Journal of Chemical Physics, Vol. 114, Issue 13
Left-right correlation energy
journal, March 2001
- Handy, Nicholas C.; Cohen, Aron J.
- Molecular Physics, Vol. 99, Issue 5
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008
- Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I.
- Physical Review Letters, Vol. 100, Issue 13
Toward improved density functionals for the correlation energy
journal, October 2009
- Thakkar, Ajit J.; McCarthy, Shane P.
- The Journal of Chemical Physics, Vol. 131, Issue 13
Generalized Gradient Approximation That Recovers the Second-Order Density-Gradient Expansion with Optimized Across-the-Board Performance
journal, July 2011
- Peverati, Roberto; Zhao, Yan; Truhlar, Donald G.
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 16
HLE16: A Local Kohn–Sham Gradient Approximation with Good Performance for Semiconductor Band Gaps and Molecular Excitation Energies
journal, January 2017
- Verma, Pragya; Truhlar, Donald G.
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 2
Exchange–Correlation Functional with Good Accuracy for Both Structural and Energetic Properties while Depending Only on the Density and Its Gradient
journal, June 2012
- Peverati, Roberto; Truhlar, Donald G.
- Journal of Chemical Theory and Computation, Vol. 8, Issue 7
Nonseparable exchange–correlation functional for molecules, including homogeneous catalysis involving transition metals
journal, January 2015
- Yu, Haoyu S.; Zhang, Wenjing; Verma, Pragya
- Physical Chemistry Chemical Physics, Vol. 17, Issue 18
New exchange-correlation density functionals: The role of the kinetic-energy density
journal, June 2002
- Boese, A. Daniel; Handy, Nicholas C.
- The Journal of Chemical Physics, Vol. 116, Issue 22
A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006
- Zhao, Yan; Truhlar, Donald G.
- The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101
M11-L: A Local Density Functional That Provides Improved Accuracy for Electronic Structure Calculations in Chemistry and Physics
journal, December 2011
- Peverati, Roberto; Truhlar, Donald G.
- The Journal of Physical Chemistry Letters, Vol. 3, Issue 1
Semilocal and hybrid meta-generalized gradient approximations based on the understanding of the kinetic-energy-density dependence
journal, January 2013
- Sun, Jianwei; Haunschild, Robin; Xiao, Bing
- The Journal of Chemical Physics, Vol. 138, Issue 4
HLE17: An Improved Local Exchange–Correlation Functional for Computing Semiconductor Band Gaps and Molecular Excitation Energies
journal, March 2017
- Verma, Pragya; Truhlar, Donald G.
- The Journal of Physical Chemistry C, Vol. 121, Issue 13
An improved and broadly accurate local approximation to the exchange–correlation density functional: The MN12-L functional for electronic structure calculations in chemistry and physics
journal, January 2012
- Peverati, Roberto; Truhlar, Donald G.
- Physical Chemistry Chemical Physics, Vol. 14, Issue 38
MN15-L: A New Local Exchange-Correlation Functional for Kohn–Sham Density Functional Theory with Broad Accuracy for Atoms, Molecules, and Solids
journal, February 2016
- Yu, Haoyu S.; He, Xiao; Truhlar, Donald G.
- Journal of Chemical Theory and Computation, Vol. 12, Issue 3
Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993
- Becke, Axel D.
- The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994
- Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
- The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
Toward reliable adiabatic connection models free from adjustable parameters
journal, August 1997
- Adamo, C.; Barone, V.
- Chemical Physics Letters, Vol. 274, Issue 1-3
Exchange functionals with improved long-range behavior and adiabatic connection methods without adjustable parameters: The mPW and mPW1PW models
journal, January 1998
- Adamo, Carlo; Barone, Vincenzo
- The Journal of Chemical Physics, Vol. 108, Issue 2
Development and assessment of new exchange-correlation functionals
journal, October 1998
- Hamprecht, Fred A.; Cohen, Aron J.; Tozer, David J.
- The Journal of Chemical Physics, Vol. 109, Issue 15
Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999
- Adamo, Carlo; Barone, Vincenzo
- The Journal of Chemical Physics, Vol. 110, Issue 13
Adiabatic Connection for Kinetics
journal, June 2000
- Lynch, Benjamin J.; Fast, Patton L.; Harris, Maegan
- The Journal of Physical Chemistry A, Vol. 104, Issue 21
Reparameterization of hybrid functionals based on energy differences of states of different multiplicity
journal, December 2001
- Reiher, Markus; Salomon, Oliver; Artur Hess, Bernd
- Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 107, Issue 1
A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
journal, July 2004
- Yanai, Takeshi; Tew, David P.; Handy, Nicholas C.
- Chemical Physics Letters, Vol. 393, Issue 1-3, p. 51-57
Hybrid Meta Density Functional Theory Methods for Thermochemistry, Thermochemical Kinetics, and Noncovalent Interactions: The MPW1B95 and MPWB1K Models and Comparative Assessments for Hydrogen Bonding and van der Waals Interactions
journal, August 2004
- Zhao, Yan; Truhlar, Donald G.
- The Journal of Physical Chemistry A, Vol. 108, Issue 33
Semiempirical hybrid functional with improved performance in an extensive chemical assessment
journal, September 2005
- Keal, Thomas W.; Tozer, David J.
- The Journal of Chemical Physics, Vol. 123, Issue 12
Assessment of a long-range corrected hybrid functional
journal, December 2006
- Vydrov, Oleg A.; Scuseria, Gustavo E.
- The Journal of Chemical Physics, Vol. 125, Issue 23
Can short-range hybrids describe long-range-dependent properties?
journal, July 2009
- Henderson, Thomas M.; Izmaylov, Artur F.; Scalmani, Giovanni
- The Journal of Chemical Physics, Vol. 131, Issue 4
Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006
- Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.
- The Journal of Chemical Physics, Vol. 125, Issue 22
Communication: A global hybrid generalized gradient approximation to the exchange-correlation functional that satisfies the second-order density-gradient constraint and has broad applicability in chemistry
journal, November 2011
- Peverati, Roberto; Truhlar, Donald G.
- The Journal of Chemical Physics, Vol. 135, Issue 19
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010
- Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
- The Journal of Chemical Physics, Vol. 132, Issue 15
Effect of the damping function in dispersion corrected density functional theory
journal, March 2011
- Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars
- Journal of Computational Chemistry, Vol. 32, Issue 7
Screened-exchange density functionals with broad accuracy for chemistry and solid-state physics
journal, January 2012
- Peverati, Roberto; Truhlar, Donald G.
- Physical Chemistry Chemical Physics, Vol. 14, Issue 47
Comparative assessment of a new nonempirical density functional: Molecules and hydrogen-bonded complexes
journal, December 2003
- Staroverov, Viktor N.; Scuseria, Gustavo E.; Tao, Jianmin
- The Journal of Chemical Physics, Vol. 119, Issue 23
Exchange-correlation functional with broad accuracy for metallic and nonmetallic compounds, kinetics, and noncovalent interactions
journal, October 2005
- Zhao, Yan; Schultz, Nathan E.; Truhlar, D. G.
- The Journal of Chemical Physics, Vol. 123, Issue 16
Design of Density Functionals by Combining the Method of Constraint Satisfaction with Parametrization for Thermochemistry, Thermochemical Kinetics, and Noncovalent Interactions
journal, January 2006
- Zhao, Yan; Schultz, Nathan E.; Truhlar, Donald G.
- Journal of Chemical Theory and Computation, Vol. 2, Issue 2
Design of Density Functionals That Are Broadly Accurate for Thermochemistry, Thermochemical Kinetics, and Nonbonded Interactions
journal, June 2005
- Zhao, Yan; Truhlar, Donald G.
- The Journal of Physical Chemistry A, Vol. 109, Issue 25
Density Functional for Spectroscopy: No Long-Range Self-Interaction Error, Good Performance for Rydberg and Charge-Transfer States, and Better Performance on Average than B3LYP for Ground States
journal, December 2006
- Zhao, Yan; Truhlar, Donald G.
- The Journal of Physical Chemistry A, Vol. 110, Issue 49
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals
journal, July 2007
- Zhao, Yan; Truhlar, Donald G.
- Theoretical Chemistry Accounts, Vol. 120, Issue 1-3
Exploring the Limit of Accuracy of the Global Hybrid Meta Density Functional for Main-Group Thermochemistry, Kinetics, and Noncovalent Interactions
journal, October 2008
- Zhao, Yan; Truhlar, Donald G.
- Journal of Chemical Theory and Computation, Vol. 4, Issue 11
Improving the Accuracy of Hybrid Meta-GGA Density Functionals by Range Separation
journal, October 2011
- Peverati, Roberto; Truhlar, Donald G.
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 21