Seven useful questions in density functional theory

Crisostomo, Steven; Pederson, Ryan; Kozlowski, John; Kalita, Bhupalee; Cancio, Antonio C.; Datchev, Kiril; Wasserman, Adam; Song, Suhwan; Burke, Kieron

doi:10.1007/s11005-023-01665-z

Cited by 7 publications

(4 citation statements)

References 166 publications

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“…Overall, our presented methods provide simple and effective solutions for improving density functional evaluations. As Burke and co-workers have noted, even small improvements in our current density functional approximations can have a significant impact on applications in science and technology. Therefore, we hope that our contributions will lead to more widespread application of DC(HF)-DFT and C(HF)-DFT, and in that way have a positive impact on quantum chemical applications of all kinds.…”

Section: Discussionmentioning

confidence: 99%

“…There is a further source of error cancellation in the density sensitivity measure: since the density sensitivity is measured using an approximate exchange-correlation functional, errors in that functional can cancel the ones in the density as functional errors and density-driven errors have opposite signs . That such an error cancellation can occur is well-known. ,, …”

Section: Theoretical Considerationsmentioning

confidence: 99%

“…43 That such an error cancellation can occur is well-known. 29,56,67 In that context, we also mention the work of Kepp, who proposed a recipe to assess the degree of normality that evaluates four distinct functionals on each other's selfconsistent densities. 68 The use of various functionals reduces the probability of error cancellation in measuring the abnormality of the reaction.…”

Section: ■ Introductionmentioning

confidence: 99%

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Simple and Efficient Route toward Improved Energetics within the Framework of Density-Corrected Density Functional Theory

Gräf

Thom

2023

J. Chem. Theory Comput.

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The crucial step in density-corrected Hartree–Fock density functional theory (DC(HF)-DFT) is to decide whether the density produced by the density functional for a specific calculation is erroneous and, hence, should be replaced by, in this case, the HF density. We introduce an indicator, based on the difference in noninteracting kinetic energies between DFT and HF calculations, to determine when the HF density is the better option. Our kinetic energy indicator directly compares the self-consistent density of the analyzed functional with the HF density, is size-intensive, reliable, and most importantly highly efficient. Moreover, we present a procedure that makes best use of the computed quantities necessary for DC(HF)-DFT by additionally evaluating a related hybrid functional and, in that way, not only “corrects” the density but also the functional itself; we call that procedure corrected Hartree–Fock density functional theory (C(HF)-DFT).

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Section: Discussionmentioning

confidence: 99%

Section: Theoretical Considerationsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Simple and Efficient Route toward Improved Energetics within the Framework of Density-Corrected Density Functional Theory

Gräf

Thom

2023

J. Chem. Theory Comput.

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“…To determine when one should throw out the self-consistent density, the concept of density sensitivity ( S̃ ) was introduced, which is practically quantifiable as S̃ = | Ẽ false[ n normalL D A false] − Ẽ false[ n normalH F false] | where Ẽ is the DFA of interest and n LDA and n HF are the electron densities obtained by LDA and HF, respectively. A density sensitivity over 2 kcal/mol provides a practical guide for when self-consistent densities are likely problematic. ,, This generic rule works well for covalent bonds in small molecules but must be modified for weaker bonds or bigger molecules. Other metrics to evaluate density sensitivity have been proposed, , and a suitable method for the context should be chosen.…”

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confidence: 99%

Density-Corrected Density Functional Theory for Open Shells: How to Deal with Spin Contamination

Yu,

Song,

Nam

et al. 2023

J. Phys. Chem. Lett.

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Density functional theory (DFT) is usually used self-consistently to predict chemical properties, but the use of the Hartree–Fock (HF) density improves energetics in certain, well-characterized cases. Density-corrected (DC) DFT provides the theory behind this, but unrestricted Hartree–Fock (UHF) densities yield poor energetics in cases of strong spin contamination. Here we compare with restricted open-shell HF (ROHF) across 13 different functionals and two DC-DFT methods. For significant spin contamination, ROHF densities outperform UHF densities by as much as a factor of 3, depending on the energy functional, and ROHF-DFT improves over self-consistent DFT for most of the tested functionals. We refine the DC(HF)-DFT algorithm to use ROHF densities in cases of severe spin contamination.

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Exchange correlation potentials from full configuration interaction in a Slater orbital basis

Tribedi,

Dang,

Kanungo

et al. 2023

The Journal of Chemical Physics

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Ryabinkin–Kohut–Staroverov (RKS) theory builds a bridge between wave function theory and density functional theory by using quantities from the former to produce accurate exchange-correlation potentials needed by the latter. In this work, the RKS method is developed and tested alongside Slater atomic orbital basis functions for the first time. To evaluate this approach, full configuration interaction computations in the Slater orbital basis are employed to give quality input to RKS, allowing full correlation to be present along with correct nuclei cusps and asymptotic decay of the wavefunction. SlaterRKS is shown to be an efficient algorithm to arrive at exchange-correlation potentials without unphysical artifacts in moderately-sized basis sets. Furthermore, enforcement of the nuclear cusp conditions will be shown to be vital for the success of the Slater-basis RKS method. Examples of weakly and strongly correlated molecular systems will demonstrate the main features of SlaterRKS.

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Seven useful questions in density functional theory

Cited by 7 publications

References 166 publications

Simple and Efficient Route toward Improved Energetics within the Framework of Density-Corrected Density Functional Theory

Simple and Efficient Route toward Improved Energetics within the Framework of Density-Corrected Density Functional Theory

Density-Corrected Density Functional Theory for Open Shells: How to Deal with Spin Contamination

Exchange correlation potentials from full configuration interaction in a Slater orbital basis

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