Range-separated double-hybrid density-functional theory applied to periodic systems

Sansone, Giuseppe; Civalleri, Bartolomeo; Usvyat, Denis; Toulouse, Julien; Sharkas, Kamal; Maschio, Lorenzo

doi:10.1063/1.4922996

Cited by 23 publications

(21 citation statements)

References 135 publications

(170 reference statements)

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“…[28][29][30][31] Molecular crystals represents an ideal benchmark to evaluate the accuracy of the theoretical prediction of intermolecular forces in solid-state. Computing cohesive energy and optimized cell volume of molecular crystals is nowadays affordable for medium-to-large molecular crystals and the comparison with experiment is facilitated because of the richness of available data.…”

Section: Introductionmentioning

confidence: 99%

Assessment of Different Quantum Mechanical Methods for the Prediction of Structure and Cohesive Energy of Molecular Crystals

Cutini

Civalleri

Corno

et al. 2016

J. Chem. Theory Comput.

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147

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A comparative assessment of the accuracy of different quantum mechanical methods for evaluating the structure and the cohesive energy of molecular crystals is presented. In particular, we evaluate the performance of the semiempirical HF-3c method in comparison with the B3LYP-D* and the Local MP2 (LMP2) methods by means of a fully periodic approach. Three benchmark sets have been investigated: X23, G60, and the new K7; for a total of 82 molecular crystals. The original HF-3c method performs well but shows a tendency at overbinding molecular crystals, in particular for weakly bounded systems. For the X23 set, the mean absolute error for the cohesive energies computed with the HF-3c method is comparable to the LMP2 one. A refinement of the HF-3c has been attempted by tuning the dispersion term in the HF-3c energy. While the performance on cohesive energy prediction slightly worsens, optimized unit cell volumes are in excellent agreement with experiment. Overall, the B3LYP-D* method combined with a TZP basis set gives the best results. For cost-effective calculations on molecular crystals, we propose to compute cohesive energies at the B3LYP-D*/TZP level of theory on the dispersion-scaled HF-3c optimized geometries (i.e., B3LYP-D*/TZP//HF-3c(0.27) also dubbed as SP-B3LYP-D*). Besides, for further benchmarking on molecular crystals, we propose to combine the three test sets in a new one denoted as MC82.

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Section: Introductionmentioning

confidence: 99%

Assessment of Different Quantum Mechanical Methods for the Prediction of Structure and Cohesive Energy of Molecular Crystals

Cutini

Civalleri

Corno

et al. 2016

J. Chem. Theory Comput.

Self Cite

147

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“…Recent advent of the first‐principles computations can be illustrated by benchmarking calculations of molecular interactions by wavefunction ab initio or quantum Monte Carlo methods. Reliability of such calculations enabled successful calculations of the cohesive energies ( E coh ) of various molecular crystals using either periodic local MP2, random phase approximation, DFT calculations with reliable functionals or semi‐empiric corrections for dispersion, or fragment‐based ab initio techniques. .…”

Section: Introductionmentioning

confidence: 99%

Sublimation Properties of α,ω‐Diamines Revisited from First‐Principles Calculations

Červinka

Štejfa

2020

ChemPhysChem

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Sublimation enthalpies of alkane‐α,ω‐diamines exhibit an odd‐even pattern within their homologous series. First‐principles calculations coupled with the quasi‐harmonic approximation for crystals and with the conformation mixing model for the ideal gas are used to explain this phenomenon from the theoretical point of view. Crystals of the odd and even alkane‐α,ω‐diamines distinctly differ in their packing motifs. However, first‐principles calculations indicate that it is a delicate interplay of the cohesive forces, phonons, molecular vibrations and conformational equilibrium which governs the odd‐even pattern of the sublimation enthalpies within the homologous series. High molecular flexibility of the alkane‐α,ω‐diamines predetermines higher sensitivity of the computational model to the quality of the optimized geometries and relative conformational energies. Performance of high‐throughput computational methods, such as the density functional tight binding (DFTB, GFN2‐xTB) and the explicitly correlated dispersion‐corrected Møller‐Plesset perturbative method (MP2C‐F12), are benchmarked against the consistent state‐of‐the‐art calculations of conformational energies and interaction energies, respectively.

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“…Double hybrids are probably unsuitable for metallic solids96 , due to divergence problems that could derive from the PT2 terms but they are rather promising for molecular crystals (see for instance reference 97). A recent paper proposed a RSX-DH approach applied to solids and the results are encouraging, albeit only a few systems were tested98 . Since efficient implementations of perturbative approach within Periodic Boundary Conditions were done both with Gaussian and planewave basis sets99,100 , opening the perspectives of more systematic tests of both DHs and RSX-DHs functionals, we expect that a definitive answer on their use for solid state could be assessed in the near future.…”

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confidence: 99%

Range-Separated Double-Hybrid Functional from Nonempirical Constraints

Brémond

Savarese

Pérez-Jiménez

et al. 2018

J. Chem. Theory Comput.

133

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On the basis of our previous developments in the field of nonempirical double hybrids, we present here a new exchange-correlation functional based on a range-separated model for the exchange part and integrating a nonlocal perturbative correction to the electron correlation contribution. Named RSX-QIDH, the functional is free from any kind of empirical parametrization. Its range-separation parameter is set to recover the total energy of the hydrogen atom, thus eliminating the self-interaction error for this one-electron system. Subsequent tests on some relevant benchmark data sets confirm that the self-interaction error is particularly low for RSX-QIDH. This new functional provides also correct dissociation profiles for charged rare-gas dimers and very accurate ionization potentials directly from Kohn-Sham orbital energies. Above all, these good results are not obtained at the expense of other properties. Indeed, further tests on standard benchmarks show that RSX-QIDH is competitive with the more empirical ωB97X-2 double hybrid and outperforms the parent LC-PBE long-range corrected hybrid, thus underlining the important role of the nonlocal perturbative correlation.

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Range-separated double-hybrid density-functional theory applied to periodic systems

Cited by 23 publications

References 135 publications

Assessment of Different Quantum Mechanical Methods for the Prediction of Structure and Cohesive Energy of Molecular Crystals

Assessment of Different Quantum Mechanical Methods for the Prediction of Structure and Cohesive Energy of Molecular Crystals

Sublimation Properties of α,ω‐Diamines Revisited from First‐Principles Calculations

Range-Separated Double-Hybrid Functional from Nonempirical Constraints

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