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

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

doi:10.1021/acs.jpca.6b00994

Cited by 33 publications

(46 citation statements)

References 62 publications

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“…For instance, the orbital optimization scheme, i.e. the self-consistent minimization of the total energy with respect to changes in orbitals, has been recently applied to the PBE0-DH and QI-DH schemes 18,19 . In both cases, the modest impact found on the accuracy is counterbalanced by a significant increase of the computation times, making these methods unaffordable for larger systems, though interesting for difficult open-shell cases.…”

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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Section: Fine Tuningmentioning

confidence: 99%

Nonempirical Double-Hybrid Functionals: An Effective Tool for Chemists

et al. 2016

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“…Like for regular orbital-optimized MP2 method, also here the optimization of orbitals leads to substantial improvements in spin-unrestricted calculations for symmetry breaking and open-shell situations. Very recently, an approximate orbital-optimized DH scheme was also proposed which confirmed the utility of optimizing the orbitals in complicated electronicstructure problems [10].…”

Section: For a Review) In General Dh Approximationsmentioning

confidence: 83%

“…(10) and (11)], the EXX and GL2 potentials are calculated using expansions in a finite Gaussian basis set [38][39][40][41][42]. The EXX potential is thus expanded over orthonormalized auxiliary Gaussian basis functions {g n (r)} as…”

Section: B Self-consistent Oep Double-hybrid Approximationsmentioning

confidence: 99%

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Self-consistent double-hybrid density-functional theory using the optimized-effective-potential method

Śmiga

Franck

Mussard

et al. 2016

The Journal of Chemical Physics

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We introduce an orbital-optimized double-hybrid (DH) scheme using the optimized-effectivepotential (OEP) method. The orbitals are optimized using a local potential corresponding to the complete exchange-correlation energy expression including the second-order Møller-Plesset (MP2) correlation contribution. We have implemented a one-parameter version of this OEP-based selfconsistent DH scheme using the BLYP density-functional approximation and compared it to the corresponding non-self-consistent DH scheme for calculations on a few closed-shell atoms and molecules. While the OEP-based self-consistency does not provide any improvement for the calculations of ground-state total energies and ionization potentials, it does improve the accuracy of electron affinities and restores the meaning of the LUMO orbital energy as being connected to a neutral excitation energy. Moreover, the OEP-based self-consistent DH scheme provides reasonably accurate exchangecorrelation potentials and correlated densities.

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“…Once these orbitals are converged, they are used to calculate the

E_{c}^{PT 2}

correlation energy which is added a posteriori to the total energy. This procedure is known to work reasonably well except for some difficult (e.g., open‐shell or symmetry‐breaking) cases, as it was also documented before for hybrid density functionals, where the results can be improved by an orbital‐optimized scheme to obtain a set of orbitals built under the influence of the perturbative field too . Another successful approach circumvents these caveats using the orbitals generated by a hybrid model (e.g., the PBE0 functional) directly into the DH expression, giving rise to the family of xDH functionals .…”

Section: Introductionmentioning

confidence: 80%

Determining the role of the underlying orbital‐dependence of PBE0‐DH and PBE‐QIDH double‐hybrid density functionals

et al. 2017

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We study the orbital-dependence of three (parameter-free) double-hybrid density functionals, namely the PBE0-DH, the PBE-QIDH models, and the SOS1-PBE-QIDH spin-opposite-scaled variant of the latter. To do it, we feed all their energy terms with different sets of orbitals obtained previously from self-consistent density functional theory calculations using several exchange-correlation functionals (e.g., PBE, PBE0, PBEH&H), or directly with HF-PBE orbitals, to see their effect on selected datasets for atomization and reaction energies, the latter proned to marked self-interaction errors. We find that the PBE-QIDH double-hybrid model shows a great consistency, as the best results are always obtained for the set of orbitals corresponding to its hybrid scheme, which prompts us to recommend this model without any other fitting or reparameterization. © 2017 Wiley Periodicals, Inc.

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

Cited by 33 publications

References 62 publications

Nonempirical Double-Hybrid Functionals: An Effective Tool for Chemists

Nonempirical Double-Hybrid Functionals: An Effective Tool for Chemists

Self-consistent double-hybrid density-functional theory using the optimized-effective-potential method

Determining the role of the underlying orbital‐dependence of PBE0‐DH and PBE‐QIDH double‐hybrid density functionals

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