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

  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},
  volume={14 4},
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… 

Figures and Tables from this paper

How accurate are static polarizability predictions from density functional theory? An assessment over 132 species at equilibrium geometry.
A database of benchmark static polarizabilities for 132 small species at equilibrium geometry is developed, using coupled cluster theory through triple excitations (extrapolated to the complete basis set limit), for the purpose of developing and assessing density functionals.
Dipole Moment Calculations Using Multiconfiguration Pair-Density Functional Theory and Hybrid Multiconfiguration Pair-Density Functional Theory.
The dipole moment is the molecular property that most directly indicates molecular polarity. The accuracy of computed dipole moments depends strongly on the quality of the calculated electron
The effect of self-interaction error on electrostatic dipoles calculated using density functional theory.
It is found that correcting for self-interaction generally increases the degree of charge transfer, thereby increasing the size of calculated dipole moments, and the best agreement between the FLO-SIC-DFA and reference dipoles occurs when the molecular geometries are optimized using the FL olympic orbital approach.
On the Computation of Dipole Moments: A Recommendation on the Choice of the Basis Set and the Level of Theory.
The results indicate that the best compromise between accuracy and computational efficiency is achieved by performing the computations with an augmented double zeta-quality basis set, and highlight the crucial role that augmentation of the basis set with diffuse functions on both hydrogen and non-hydrogen atoms plays in the computation of dipole moments.
Benchmarking Semiempirical QM Methods for Calculating the Dipole Moment of Organic Molecules.
The dipole moment is a simple descriptor of the charge distribution and polarity and is important for understanding and predicting various molecular properties. Semiempirical (SE) methods offer a
Basis-set correction for coupled-cluster estimation of dipole moments.
The present work proposes an approach to obtain a basis-set correction based on density-functional theory (DFT) for the computation of molecular properties in wave-function theory (WFT). This
Benchmarking Electronic Structure Methods for Accurate Fixed-Charge Electrostatic Models
It is demonstrated that using computationally inexpensive density functional theory (DFT) methods, together with appropriate augmented basis sets and a continuum solvent model, can yield molecular dipole moments that are both more strongly and more uniformly overpolarized.
Predicting molecular dipole moments by combining atomic partial charges and atomic dipoles.
The resulting "MuML" models are fitted together to reproduce molecular μ computed using high-level coupled-cluster theory and density functional theory on the QM7b dataset, achieving more accurate results due to the physics-based combination of these complementary terms.
Evaluation of Local Hybrid Functionals for Electric Properties: Dipole Moments and Static/Dynamic Polarizabilities.
Comparisons with coupled-cluster benchmark data show robust performance of all investigated local hybrids for dipole moments and polarizabilities, and the currently most highly parameterized LH20t clearly produces not only good energetics but also accurate electron densities and electric-field response.
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.
It is shown that the XYG3 and XYGJ-OS functionals can be ill behaved for stretched bonds well beyond the Coulson-Fischer point, predicting unphysical dipole moments and humps in potential energy curves for some simple systems like the hydrogen fluoride molecule.


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