Dispersion corrections applied to the TCA family of exchange-correlation functionals

Fabiano, Eduardo; Cortona, Pietro

doi:10.1007/s00214-017-2120-0

Cited by 6 publications

(5 citation statements)

References 79 publications

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“…Moreover, for non-polar complexes and/or at large intermolecular distances, where covalent interactions are negligible, they play a dominant role. For these reasons, the proper description of dispersion as well as other non-covalent forces has gained a prominent role in computational chemistry [6,[10][11][12][13][14][15][16]. Even more important is the role they play in solid-state applications where extended systems are involved, whose cohesion is not mainly determined by iono-covalent interactions [3,5,8,9,[17][18][19][20][21], e.g., layered or molecular solids.…”

Section: Introductionmentioning

confidence: 99%

Solid-State Testing of a Van-Der-Waals-Corrected Exchange-Correlation Functional Based on the Semiclassical Atom Theory

et al. 2018

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Abstract:We extend the SG4 generalized gradient approximation, developed for covalent and ionic solids with a nonlocal van der Waals functional. The resulting SG4-rVV10m functional is tested, considering two possible parameterizations, for various kinds of bulk solids including layered materials and molecular crystals as well as regular bulk materials. The results are compared to those of similar methods, PBE + rVV10L and rVV10. In most cases, SG4-rVV10m yields a quite good description of systems (from iono-covalent to hydrogen-bond and dispersion interactions), being competitive with PBE + rVV10L and rVV10 for dispersion-dominated systems and slightly superior for iono-covalent ones. Thus, it shows a promising applicability for solid-state applications. In a few cases, however, overbinding is observed. This is analysed in terms of gradient contributions to the functional.

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Section: Introductionmentioning

confidence: 99%

Solid-State Testing of a Van-Der-Waals-Corrected Exchange-Correlation Functional Based on the Semiclassical Atom Theory

et al. 2018

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“…An accurate description of noncovalent interactions (NCIs) is crucial for fields ranging from chemistry to biology to materials science, with a plethora of methods being constantly developed, tested, and improved. − Second-order Møller–Plesset (MP2) perturbation theory has been often considered a relatively safe choice for the treatment of NCIs in chemistry, given its favorable scaling relative to more sophisticated wave function methods and encouraging early successes in capturing NCIs in small systems. , The described failures of MP2 when applied to NCIs, such as those in stacking complexes, have been often considered accidental. Very recently, Furche and co-workers have shown that MP2 relative errors for NCIs can grow systematically with molecular size and that the whole MP series may be even qualitatively unsuitable for the description of large noncovalent complexes.…”

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confidence: 99%

Noncovalent Interactions from Models for the Møller–Plesset Adiabatic Connection

Daas

Fabiano

Sala

et al. 2021

J. Phys. Chem. Lett.

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Given the omnipresence of noncovalent interactions (NCIs), their accurate simulations are of crucial importance across various scientific disciplines. Here we construct accurate models for the description of NCIs by an interpolation along the Møller–Plesset adiabatic connection (MP AC). Our interpolation approximates the correlation energy, by recovering MP2 at small coupling strengths and the correct large-coupling strength expansion of the MP AC, recently shown to be a functional of the Hartree–Fock density. Our models are size consistent for fragments with nondegenerate ground states, have the same cost as double hybrids, and require no dispersion corrections to capture NCIs accurately. These interpolations greatly reduce large MP2 errors for typical π-stacking complexes (e.g., benzene–pyridine dimers) and for the L7 data set. They are also competitive with state-of-the-art dispersion enhanced functionals and can even significantly outperform them for a variety of data sets, such as CT7 and L7.

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“…Noncovalant interactions (NCIs) play a crucial role in a variety of fields including biology, chemistry, material science, and everything in between. − Second order Møller–Plesset perturbation theory (MP2) has been used extensively to study NCIs , because it includes dispersion interactions and also has more favorable scalings compared to other wave function methods such as CCSD(T). However, MP2 does have its downsides, because it is known to fail for π–π stacking complexes and generally for NCIs involving highly polarizable molecules .…”

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confidence: 99%

Regularized and Opposite Spin-Scaled Functionals from Møller–Plesset Adiabatic Connection─Higher Accuracy at Lower Cost

Daas,

Kooi,

Peters

et al. 2023

J. Phys. Chem. Lett.

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Noncovalent interactions (NCIs) play a crucial role in biology, chemistry, material science, and everything in between. To improve pure quantum-chemical simulations of NCIs, we propose a methodology for constructing approximate correlation energies by combining an interpolation along the Møller−Plesset adiabatic connection (MP AC) with a regularization and spin-scaling strategy applied to MP2 correlation energies. This combination yields c os κ os -SPL2, which exhibits superior accuracy for NCIs compared to any of the individual strategies. With the N 4 formal scaling, c os κ os -SPL2 is competitive or often outperforms more expensive dispersion-corrected double hybrids for NCIs. The accuracy of c os κ os -SPL2 particularly shines for anionic halogen bonded complexes, where it surpasses standard dispersion-corrected DFT by a factor of 3 to 5.

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Dispersion corrections applied to the TCA family of exchange-correlation functionals

Cited by 6 publications

References 79 publications

Solid-State Testing of a Van-Der-Waals-Corrected Exchange-Correlation Functional Based on the Semiclassical Atom Theory

Solid-State Testing of a Van-Der-Waals-Corrected Exchange-Correlation Functional Based on the Semiclassical Atom Theory

Noncovalent Interactions from Models for the Møller–Plesset Adiabatic Connection

Regularized and Opposite Spin-Scaled Functionals from Møller–Plesset Adiabatic Connection─Higher Accuracy at Lower Cost

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