Insight into organic reactions from the direct random phase approximation and its corrections

Ruzsinszky, Adrienn; Zhang, Igor Ying; Scheffler, Matthias

doi:10.1063/1.4932306

Cited by 11 publications

(15 citation statements)

References 88 publications

(139 reference statements)

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“…These reactions are also part of the large GMTKN30 database and are known to be challenging to modern semilocal density functionals . The results of PBE-QIDH and OO-PBE-QIDH calculations are gathered in Table , finding again similar results for both methods and in line with those obtained using other sophisticated methods, although more accurate results (MAD of 5.01 and RMSD of 5.31 kcal/mol) are found when parametrized double-hybrid methods like B2-PLYP are employed.…”

Section: Results and Discussionsupporting

confidence: 66%

Importance of Orbital Optimization for Double-Hybrid Density Functionals: Application of the OO-PBE-QIDH Model for Closed- and Open-Shell Systems

et al. 2016

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We assess here the reliability of orbital optimization for modern double-hybrid density functionals such as the parameter-free PBE-QIDH model. We select for that purpose a set of closed-and openshell strongly and weakly bound systems, including some standard and widely used datasets, to show that orbital optimization improves the results with respect to standard models, notably for electronically complicated systems, and through first-order properties obtained as derivatives of the energy.

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Section: Results and Discussionsupporting

confidence: 66%

Importance of Orbital Optimization for Double-Hybrid Density Functionals: Application of the OO-PBE-QIDH Model for Closed- and Open-Shell Systems

et al. 2016

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“…This reaction is an isomerization, while all others in SIE11 are dissociations. Many authors ,, noticed that the isomerization energy of ClFCl to ClClF is a difficult case for many functionals. Table shows that the FLOSIC-LSDA/-PBE calculations have SEs of only 4.6/2.0 kcal/mol, leading to a significant improvement over the LSDA/PBE functionals (SE = 30/23 kcal/mol), respectively.…”

Section: Resultsmentioning

confidence: 99%

Shrinking Self-Interaction Errors with the Fermi–Löwdin Orbital Self-Interaction-Corrected Density Functional Approximation

Sharkas

Trepte

et al. 2018

J. Phys. Chem. A

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The self-interaction error (SIE) is one of the major drawbacks of practical exchange-correlation functionals for Kohn–Sham density functional theory. Despite this, the use of methods that explicitly remove SIE from approximate density functionals is scarce in the literature due to their relatively high computational cost and lack of consistent improvement over standard modern functionals. In this article we assess the performance of a novel approach recently proposed by Pederson, Ruzsinszky, and Perdew [J. Chem. Phys. 2014, 140, 121103] for performing self-interaction free calculations in density functional theory based on Fermi orbitals. To this end, we employ test sets consisting of reaction energies that are considered particularly sensitive to SIE. We found that the parameter-free Fermi–Löwdin orbital self-interaction correction method combined with the standard local spin density approximation (LSDA) and Perdew–Burke–Ernzerhof (PBE) functionals gives a much better estimate of reaction energies compared to their parent LSDA and PBE functionals for most of the reactions in these two sets. They also perform on par with the global PBE0 and range-separated LC-ωPBE hybrids, which partially eliminate the SIE by including Hartree–Fock exchange. This shows the potential of the Fermi–Löwdin orbital self-interaction correction (FLOSIC) method for practical density functional calculations without SIE.

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“…It is also true for dRPA and pure PT2 because these methods use a full portion of the HF‐like exchange. However, as suggested in Figure 2a, dRPA produces an even worse

H_{2}^{+}

dissociation curve than lower‐rung DFAs, indicating that dRPA contains very heavy SIE in its correlation part (also called self‐correlation error 107 ).…”

Section: Challengesmentioning

confidence: 91%

On the top rung of Jacob's ladder of density functional theory: Toward resolving the dilemma of SIE and NCE

Zhang

2020

WIREs Comput Mol Sci

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According to the classification of Jacob's Ladder proposed by Perdew, density functional approximations (DFAs) on the top (fifth) rung add the information of the unoccupied Kohn-Sham orbitals, which hold the promise to enter the heaven of chemical accuracy. In other words, we expect that a much higher accuracy with a broader applicability than the existing DFAs would eventually be achieved on the fifth rung. Nonetheless, Jacob's Ladder itself does not offer a recipe for how to manipulate the unoccupied Kohn-Sham orbitals on the construction of a successful fifth rung DFA. In this article, we briefly review two successful types of the fifth rung DFAs, that is, random-phase approximation (RPA) and doubly hybrid approximation (DHA). The limitations of RPA and DHA will be introduced in the context of the so-called self-interaction error (SIE)/nondynamic correlation error (NCE) dilemma in the world of density functional theory. We propose the development strategy for DHAs to address the general concern about the future of advanced DFAs on the fifth rung. We share our experience here, based on the relevant efforts recently made by the authors and their co-workers, aiming to resolve the SIE/NCE dilemma and to extend the applicability of DHAs from the chemistry of the main group elements to that of the transition metals.

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Insight into organic reactions from the direct random phase approximation and its corrections

Cited by 11 publications

References 88 publications

Importance of Orbital Optimization for Double-Hybrid Density Functionals: Application of the OO-PBE-QIDH Model for Closed- and Open-Shell Systems

Importance of Orbital Optimization for Double-Hybrid Density Functionals: Application of the OO-PBE-QIDH Model for Closed- and Open-Shell Systems

Shrinking Self-Interaction Errors with the Fermi–Löwdin Orbital Self-Interaction-Corrected Density Functional Approximation

On the top rung of Jacob's ladder of density functional theory: Toward resolving the dilemma of SIE and NCE

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