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Title: How Accurate Is Density Functional Theory at Predicting Dipole Moments? An Assessment Using a New Database of 200 Benchmark Values

Journal Article · · Journal of Chemical Theory and Computation
ORCiD logo [1]; ORCiD logo [2]
  1. Univ. of California, Berkeley, CA (United States). Kenneth S. Pitzer Center for Theoretical Chemistry, Department of Chemistry
  2. Univ. of California, Berkeley, CA (United States). Kenneth S. Pitzer Center for Theoretical Chemistry, Department of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
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We present that dipole moments are a simple, global measure of the accuracy of the electron density of a polar molecule. Dipole moments also affect the interactions of a molecule with other molecules as well as electric fields. To directly assess the accuracy of modern density functionals for calculating dipole moments, we have developed a database of 200 benchmark dipole moments, using coupled cluster theory through triple excitations, extrapolated to the complete basis set limit. This new database is used to assess the performance of 88 popular or recently developed density functionals. The results suggest that double hybrid functionals perform the best, yielding dipole moments within about 3.6-4.5% regularized RMS error versus the reference values - which is not very different from the 4% regularized RMS error produced by coupled cluster singles and doubles. Many hybrid functionals also perform quite well, generating regularized RMS errors in the 5-6% range. Lastly, some functionals, however, exhibit large outliers, and local functionals in general perform less well than hybrids or double hybrids.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1477282
Journal Information:
Journal of Chemical Theory and Computation, Vol. 14, Issue 4; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 131 works
Citation information provided by
Web of Science

References (119)

Generalized Gradient Approximation Made Simple journal October 1996
Binding in Radical-Solvent Binary Complexes: Benchmark Energies and Performance of Approximate Methods journal February 2013
Systematic optimization of long-range corrected hybrid density functionals journal February 2008
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
Self-interaction error of local density functionals for alkali–halide dissociation journal April 2006
Semiempirical hybrid density functional with perturbative second-order correlation journal January 2006
The QTP family of consistent functionals and potentials in Kohn-Sham density functional theory journal July 2016
Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis journal August 1980
Construction of a generalized gradient approximation by restoring the density-gradient expansion and enforcing a tight Lieb–Oxford bound journal May 2008
Hybrid exchange-correlation functional determined from thermochemical data and ab initio potentials journal November 2001
New exchange-correlation density functionals: The role of the kinetic-energy density journal June 2002
New generalized gradient approximation functionals journal January 2000
Global Hybrid Functionals: A Look at the Engine under the Hood journal November 2010
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
Density functional theory is straying from the path toward the exact functional journal January 2017
Semilocal and hybrid meta-generalized gradient approximations based on the understanding of the kinetic-energy-density dependence journal January 2013
Long-range corrected double-hybrid density functionals journal November 2009
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package journal September 2014
Second-order perturbation corrections to singles and doubles coupled-cluster methods: General theory and application to the valence optimized doubles model journal September 2000
Microwave spectrum of chloroborane, BH 2 Cl journal July 1993
Polarization Consistent Basis Sets. 4:  The Elements He, Li, Be, B, Ne, Na, Mg, Al, and Ar † journal November 2007
Nonseparable exchange–correlation functional for molecules, including homogeneous catalysis involving transition metals journal January 2015
Exchange–Correlation Functional with Good Accuracy for Both Structural and Energetic Properties while Depending Only on the Density and Its Gradient journal June 2012
Self-Consistent Equations Including Exchange and Correlation Effects journal November 1965
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections journal January 2008
Conceptual Problem with Calculating Electron Densities in Finite Basis Density Functional Theory journal August 2017
Efficient use of the correlation consistent basis sets in resolution of the identity MP2 calculations journal February 2002
Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals journal April 2017
Spurious fractional charge on dissociated atoms: Pervasive and resilient self-interaction error of common density functionals journal November 2006
A long-range-corrected density functional that performs well for both ground-state properties and time-dependent density functional theory excitation energies, including charge-transfer excited states journal February 2009
A conundrum for density functional theory journal January 2017
Gaussian basis sets for use in correlated molecular calculations. VII. Valence, core-valence, and scalar relativistic basis sets for Li, Be, Na, and Mg journal May 2010
Development of density functionals for thermochemical kinetics journal August 2004
A second-order perturbative correction to the coupled-cluster singles and doubles method: CCSD(2) journal August 2001
How well do static electronic dipole polarizabilities from gas-phase experiments compare with density functional and MP2 computations? journal October 2015
Response to Comment on “Density functional theory is straying from the path toward the exact functional” journal May 2017
Perspective: Fifty years of density-functional theory in chemical physics journal May 2014
What Makes a Density Functional Approximation Good? Insights from the Left Fukui Function journal May 2017
RI-MP2: optimized auxiliary basis sets and demonstration of efficiency journal September 1998
Mapping the genome of meta-generalized gradient approximation density functionals: The search for B97M-V journal February 2015
Semiempirical GGA-type density functional constructed with a long-range dispersion correction journal January 2006
Exchange-correlation functional with broad accuracy for metallic and nonmetallic compounds, kinetics, and noncovalent interactions journal October 2005
Comparative assessment of a new nonempirical density functional: Molecules and hydrogen-bonded complexes journal December 2003
Quantum chemistry: DFT's midlife crisis journal February 2017
Revised M06-L functional for improved accuracy on chemical reaction barrier heights, noncovalent interactions, and solid-state physics journal July 2017
Semilocal density functional obeying a strongly tightened bound for exchange journal January 2015
How Well Can the M06 Suite of Functionals Describe the Electron Densities of Ne, Ne 6+ , and Ne 8+ ? journal November 2017
Polarization consistent basis sets. II. Estimating the Kohn–Sham basis set limit journal May 2002
Simultaneous benchmarking of ground- and excited-state properties with long-range-corrected density functional theory journal July 2008
Improving the Accuracy of Hybrid Meta-GGA Density Functionals by Range Separation journal October 2011
Efficient and Accurate Double-Hybrid-Meta-GGA Density Functionals—Evaluation with the Extended GMTKN30 Database for General Main Group Thermochemistry, Kinetics, and Noncovalent Interactions journal December 2010
Increasing the applicability of density functional theory. IV. Consequences of ionization-potential improved exchange-correlation potentials journal May 2014
Development of exchange-correlation functionals with minimal many-electron self-interaction error journal May 2007
Quantised Singularities in the Electromagnetic Field journal September 1931
Nonlocal van der Waals density functional: The simpler the better journal December 2010
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
Current Status of the AMOEBA Polarizable Force Field journal March 2010
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
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
mBEEF: An accurate semi-local Bayesian error estimation density functional journal April 2014
M11-L: A Local Density Functional That Provides Improved Accuracy for Electronic Structure Calculations in Chemistry and Physics journal December 2011
Electric Resonance Spectrum of NaLi journal July 1972
A note on the accuracy of KS-DFT densities journal November 2017
Exploring the Limit of Accuracy of the Global Hybrid Meta Density Functional for Main-Group Thermochemistry, Kinetics, and Noncovalent Interactions journal October 2008
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
CHARMM general force field: A force field for drug-like molecules compatible with the CHARMM all-atom additive biological force fields journal January 2009
Use of the rVV10 Nonlocal Correlation Functional in the B97M-V Density Functional: Defining B97M-rV and Related Functionals journal December 2016
Long-range corrected hybrid meta-generalized-gradient approximations with dispersion corrections journal April 2012
Is the Accuracy of Density Functional Theory for Atomization Energies and Densities in Bonding Regions Correlated? journal April 2017
Doubly hybrid density functional for accurate descriptions of nonbond interactions, thermochemistry, and thermochemical kinetics journal March 2009
SCAN-based hybrid and double-hybrid density functionals from models without fitted parameters journal January 2016
A fast doubly hybrid density functional method close to chemical accuracy using a local opposite spin ansatz journal November 2011
Benchmarking Quantum Chemical Methods for the Calculation of Molecular Dipole Moments and Polarizabilities journal May 2014
Design of Density Functionals by Combining the Method of Constraint Satisfaction with Parametrization for Thermochemistry, Thermochemical Kinetics, and Noncovalent Interactions journal January 2006
A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP) journal July 2004
Violations of N-representability from spin-unrestricted orbitals in Møller–Plesset perturbation theory and related double-hybrid density functional theory journal April 2009
Density Functional Theory: Not Quite the Right Answer for the Right Reason Yet journal April 2017
Spin-component-scaled double hybrids: An extensive search for the best fifth-rung functionals blending DFT and perturbation theory journal July 2013
Benchmark Databases for Nonbonded Interactions and Their Use To Test Density Functional Theory journal March 2005
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Microwave Spectroscopic Detection of Fluoroborane, BH2F journal March 1993
Generalized Gradient Approximation That Recovers the Second-Order Density-Gradient Expansion with Optimized Across-the-Board Performance journal July 2011
ωB97X-V: A 10-parameter, range-separated hybrid, generalized gradient approximation density functional with nonlocal correlation, designed by a survival-of-the-fittest strategy journal January 2014
Screened-exchange density functionals with broad accuracy for chemistry and solid-state physics journal January 2012
Ab initio characterization of XH3 (X = N,P). Part II. Electric, magnetic and spectroscopic properties of ammonia and phosphine journal January 2008
Long-Range Corrected Hybrid Density Functionals with Improved Dispersion Corrections journal November 2012
Influence of the exchange screening parameter on the performance of screened hybrid functionals journal December 2006
On the performance of density functional theory for symmetry-breaking problems journal March 1999
Gaussian basis sets for use in correlated molecular calculations. V. Core‐valence basis sets for boron through neon journal September 1995
Polarization consistent basis sets. V. The elements Si–Cl journal August 2004
A new parametrization of exchange–correlation generalized gradient approximation functionals journal April 2001
Density-functional approximation for the correlation energy of the inhomogeneous electron gas journal June 1986
A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions journal November 2006
Toward reliable density functional methods without adjustable parameters: The PBE0 model journal April 1999
Highly Accurate First-Principles Benchmark Data Sets for the Parametrization and Validation of Density Functional and Other Approximate Methods. Derivation of a Robust, Generally Applicable, Double-Hybrid Functional for Thermochemistry and Thermochemical Kinetics † journal December 2008
Inhomogeneous Electron Gas journal November 1964
Accurate correlation consistent basis sets for molecular core–valence correlation effects: The second row atoms Al–Ar, and the first row atoms B–Ne revisited journal December 2002
Basis-set convergence of the molecular electric dipole moment journal September 1999
ω B97M-V: A combinatorially optimized, range-separated hybrid, meta-GGA density functional with VV10 nonlocal correlation journal June 2016
Characterizing and Understanding the Remarkably Slow Basis Set Convergence of Several Minnesota Density Functionals for Intermolecular Interaction Energies journal September 2013
XXXIV. Notes on the molecular orbital treatment of the hydrogen molecule journal April 1949
Design of Density Functionals That Are Broadly Accurate for Thermochemistry, Thermochemical Kinetics, and Nonbonded Interactions journal June 2005
Density-functional thermochemistry. V. Systematic optimization of exchange-correlation functionals journal November 1997
Polarization consistent basis sets. III. The importance of diffuse functions journal November 2002
A standard grid for density functional calculations journal July 1993
Gaussian-3 (G3) theory for molecules containing first and second-row atoms journal November 1998
Development and assessment of new exchange-correlation functionals journal October 1998
Polarization consistent basis sets: Principles journal November 2001
Comment on “Density functional theory is straying from the path toward the exact functional” journal May 2017
Energy vs. density on paths toward more exact density functionals journal January 2018
Use of approximate integrals in ab initio theory. An application in MP2 energy calculations journal June 1993
A fifth-order perturbation comparison of electron correlation theories journal May 1989
Correction: MN15: A Kohn–Sham global-hybrid exchange–correlation density functional with broad accuracy for multi-reference and single-reference systems and noncovalent interactions journal January 2016
Can Kohn–Sham density functional theory predict accurate charge distributions for both single-reference and multi-reference molecules? journal January 2017
Workhorse Semilocal Density Functional for Condensed Matter Physics and Quantum Chemistry journal July 2009
Strongly Constrained and Appropriately Normed Semilocal Density Functional journal July 2015
Semilocal and Hybrid Meta-Generalized Gradient Approximations Based on the Understanding of the Kinetic-Energy-Density Dependence text January 2013
Energy vs. density on paths toward more exact density functionals preprint January 2017
Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals [Supplemental Data] fileset June 2017

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Platinum, gold, and silver standards of intermolecular interaction energy calculations journal August 2019
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Communication: xDH double hybrid functionals can be qualitatively incorrect for non-equilibrium geometries: Dipole moment inversion and barriers to radical-radical association using XYG3 and XYGJ-OS journal May 2018
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