Quadratic integrand double-hybrid made spin-component-scaled

Brémond, Éric; Savarese, Marika; Sancho‐García, Juan Carlos; Pérez-Jiménez, Ángel J.; Adamo, Carlo

doi:10.1063/1.4944465

Cited by 40 publications

(29 citation statements)

References 47 publications

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“…and B2-PLYP). At the best of our knowledge 45 , these are one of the very few sets for which there is not a systematic improvement in going from GGA to GH to DH.…”

Section: C60iso and Iso-c60 Benchmarksmentioning

confidence: 99%

Double-Hybrid Functionals and Tailored Basis Set: Fullerene (C₆₀) Dimer and Isomers as Test Cases

et al. 2019

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A computational protocol making use of Double Hybrid functionals in conjunction with a recently developed basis set tailored to reproduce non covalent interactions (hereafter named DH-SVPD) is here applied and tested for the evaluation of properties C 60 fullerenes namely intermolecular interactions in the weakly bound C 60 dimer and relative stabilities of C 60 isomers (as described by the C60ISO and iso-C60 datasets). The obtained results suggest that the DH-SVPD performance is very close to that obtained with empirical corrections and larger quadruple- basis for the C 60 dimer. In contrast, both approaches (tailored basis set and larger basis with empirical potential) do not reach the envisaged accuracy for the relative stabilities of C 60 isomers. Nevertheless, this test well underlined how the DH-SVPD basis set is able to recover the performance obtained by coupling the DH functionals with empirical dispersion corrections and larger basis set, significantly reducing the computational effort for double hybrids and thus enabling to expand their application domain to larger molecular systems.

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“…and B2-PLYP). At the best of our knowledge 45 , these are one of the very few sets for which there is not a systematic improvement in going from GGA to GH to DH.…”

Section: C60iso and Iso-c60 Benchmarksmentioning

confidence: 99%

Double-Hybrid Functionals and Tailored Basis Set: Fullerene (C₆₀) Dimer and Isomers as Test Cases

et al. 2019

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“…Another possibility of improving the performance of the MP2 approach recently explored is the so-called spin-component scaling, where Same-Spin (SS) and Opposite-Spin (OS) contribution to the MP2 energy are scaled by an empirical factor. We have recently introduced the OS variant of the QIDH functional (SOS1-QIDH) 60 , where the SS contribution is fixed a priori and the OS is embedded in the GGA part. This approach is a computationally convenient alternative to reach the accuracy of the parent QIDH functional, without losing theoretical ground, as for the mentioned OO scheme.…”

Section: Fine Tuningmentioning

confidence: 99%

Nonempirical Double-Hybrid Functionals: An Effective Tool for Chemists

et al. 2016

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ConspectusDensity Functional Theory (DFT) emerged in the last two decades as the most reliable tool the description and prediction of properties of molecular systems and extended materials, coupling in an unprecedented way high accuracy and reasonable computational cost. This success rests also on the development of more and more performing Density Functional Approximations (DFAs).Indeed, the Achilles' heel of DFT is represented by the exchange-correlation contribution to the total energy, which, being unknown, must be approximated. Since the beginning of the '90s, global hybrids (GH) functionals, where an explicit dependence of the exchange-correlation energy on model. In such a way, a whole family of non-empirical functionals, spanning on the highest rungs of the Perdew's quality scale, is now available and competitive with other -more empirical-DFAs. This is a previous version of the article published in Accounts of Chemical Research. 2016Research. , 49(8): 1503Research. -1513Research. . doi:10.1021 2 Discussion of selected cases, ranging from thermochemistry and reactions to weak interactions and excitations energies, not only show the large range of applicability of non-empirical DFAs, but also underline how increasing the number of theoretical constrains parallel with an improvement of the DFA's numerical performances. This fact further consolidates the strong theoretical framework of non-empirical DFAs.Finally, even if non-empirical DH approaches are still computationally expensive, relying on the fact that they can benefit of all technical enhancements developed for speeding-up post-HartreeFock methods, there is a substantial hope for their near future routine application to the description and prediction of complex chemical systems and reactions.

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“…51 This concept has also been applied to ground state DHDFAs on different occasions. 16,[52][53][54][55] While this does not necessarily improve the accuracy of an DHDFA, it can reduce the computational cost by exploiting a Laplace transform for the energy expression. 51,56 Herein, we apply the SCS and SOS techniques for the first time to DHDFAs to calculate electronic excitation energies.…”

Section: Introductionmentioning

confidence: 99%

Time-Dependent Double-Hybrid Density Functionals with Spin-Component and Spin-Opposite Scaling

Schwabe

Goerigk

2017

J. Chem. Theory Comput.

293

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For the first time, we combine time-dependent double-hybrid density functional approximations (TD-DHDFAs) for the calculation of electronic excitation energies with the concepts of spin-component and spin-opposite scaling (SCS/SOS) of electron-pair contributions to their nonlocal correlation components. Different flavors of this idea, ranging from standard SCS parameters to fully fitted parameter sets, are presented and tested on six different parent DHDFAs. For cross-validation, we assess those methods on three benchmark sets that cover small- to medium-sized chromophores (up to 78 atoms) and different excitation types. For this purpose, we also introduce new CC3 reference values for the popular Gordon benchmark set that we recommend using in future studies. Our results confirm that already the (unscaled) parent TD-DHDFAs are accurate and outperform some wave function methods. Further introduction of SCS/SOS eliminates extreme outliers, reduces deviation spans from reference values by up to 0.5 eV, aligns the performance of the Tamm-Dancoff approximation (TDA) to that of full TD calculations, and also enables a more balanced description of different excitation types. The best-performing TD-based methods in our cross validation have mean absolute deviations as low as 0.14 eV compared to the time- and resource-intensive CC3 approach. A very important finding is that we also obtained SOS variants with excellent performance, contrary to wave function based methods. This opens a future pathway to highly efficient methods for the optimization of excited-state geometries, particularly when paired with computing strategies such as the Laplace transform. We recommend our SCS- and SOS-based variants for further testing and subsequent applications.

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Quadratic integrand double-hybrid made spin-component-scaled

Cited by 40 publications

References 47 publications

Double-Hybrid Functionals and Tailored Basis Set: Fullerene (C₆₀) Dimer and Isomers as Test Cases

Double-Hybrid Functionals and Tailored Basis Set: Fullerene (C₆₀) Dimer and Isomers as Test Cases

Nonempirical Double-Hybrid Functionals: An Effective Tool for Chemists

Time-Dependent Double-Hybrid Density Functionals with Spin-Component and Spin-Opposite Scaling

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Quadratic integrand double-hybrid made spin-component-scaled

Cited by 40 publications

References 47 publications

Double-Hybrid Functionals and Tailored Basis Set: Fullerene (C60) Dimer and Isomers as Test Cases

Double-Hybrid Functionals and Tailored Basis Set: Fullerene (C60) Dimer and Isomers as Test Cases

Nonempirical Double-Hybrid Functionals: An Effective Tool for Chemists

Time-Dependent Double-Hybrid Density Functionals with Spin-Component and Spin-Opposite Scaling

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Product

Resources

About

Double-Hybrid Functionals and Tailored Basis Set: Fullerene (C₆₀) Dimer and Isomers as Test Cases

Double-Hybrid Functionals and Tailored Basis Set: Fullerene (C₆₀) Dimer and Isomers as Test Cases