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

@article{Hait2018HowAI, title={How Accurate Is Density Functional Theory at Predicting Dipole Moments? An Assessment Using a New Database of 200 Benchmark Values.}, author={Diptarka Hait and Martin Head‐Gordon}, journal={Journal of chemical theory and computation}, year={2018}, volume={14 4}, pages={ 1969-1981 } }

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…

## 118 Citations

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## References

SHOWING 1-10 OF 132 REFERENCES

Can Kohn-Sham density functional theory predict accurate charge distributions for both single-reference and multi-reference molecules?

- ChemistryPhysical chemistry chemical physics : PCCP
- 2017

There exists great similarity among the success rate of various functionals in predicting dipole moments, and among gradient approximations, the best overall performance is by PBE, HCTH/407, OlyP, OreLYP, and GAM, each with MUE of 0.22 D.

Is the Accuracy of Density Functional Theory for Atomization Energies and Densities in Bonding Regions Correlated?

- ChemistryThe journal of physical chemistry letters
- 2017

Analysis of electron densities in bonding regions is found to be important for the evaluation of functionals for chemical systems and for hybrid generalized gradient approximation functionals developed since the year 2000.

Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals

- Chemistry
- 2017

ABSTRACT In the past 30 years, Kohn–Sham density functional theory has emerged as the most popular electronic structure method in computational chemistry. To assess the ever-increasing number of…

How Well Can the M06 Suite of Functionals Describe the Electron Densities of Ne, Ne6+, and Ne8+?

- ChemistryJournal of chemical theory and computation
- 2017

The M06 suite of functionals is capable of providing accurate electron densities, gradients, and Laplacians using the aug-cc-pV5Z basis set, and thus it is suitable for a wide range of applications in chemistry and physics.

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.

- ChemistryThe journal of physical chemistry. A
- 2008

The optimum hybrids for hydrogen-transfer reactions, heavy-atoms transfers, nucleophilic substitutions, and unimolecular and recombination reactions are quite different from one another: out of these subsets, the heavy-atom transfer reactions are by far the most sensitive to the percentages of Hartree-Fock-type exchange y and MP2-type correlation x in an (x, y) double hybrid.

A note on the accuracy of KS-DFT densities.

- Physics, ChemistryThe Journal of chemical physics
- 2017

Some density functional approximations outperform some wave function methods and Kohn-Sham density functionals, suggesting that the KS determinant could be a better starting point for some kinds of correlated calculations.

Simultaneous benchmarking of ground- and excited-state properties with long-range-corrected density functional theory.

- ChemistryThe Journal of chemical physics
- 2008

We present benchmark calculations using several long-range-corrected (LRC) density functionals, in which Hartree-Fock exchange is incorporated asymptotically using a range-separated Coulomb operator,…

Basis-set convergence of the molecular electric dipole moment

- Chemistry
- 1999

The electric dipole moments (μ) of BH and HF are computed in conventional calculations employing different correlation-consistent basis sets at the levels of Hartree–Fock theory, second-order…

Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation.

- PhysicsPhysical review. B, Condensed matter
- 1992

A way is found to visualize and understand the nonlocality of exchange and correlation, its origins, and its physical effects as well as significant interconfigurational and interterm errors remain.

Density functional theory is straying from the path toward the exact functional

- ChemistryScience
- 2017

The energy-minimizing electron densities for atomic species, as produced by 128 historical and modern DFT functionals, were found to become closer to the exact ones until the early 2000s, when this trend was reversed by unconstrained functionals sacrificing physical rigor for the flexibility of empirical fitting.