A Comprehensive Assessment of the Effectiveness of Orbital Optimization in Double-Hybrid Density Functionals in the Treatment of Thermochemistry, Kinetics, and Noncovalent Interactions

Najibi, Asim; Goerigk, Lars

doi:10.1021/acs.jpca.8b04058

Cited by 20 publications

(26 citation statements)

References 86 publications

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“…[123] As shown in Table 4, the performances of the five tested methods without OO in our work are approximate to those of the well-performed methods with and without OO as benchmarked by Najibi and Goerigk. [123] However, the orbitaloptimized MP2.5 method [124,125] Note that the reference binding energies in the NCCE31 dataset [87][88][89] are positive, which are different from the S22 [80][81][82][83] and S66 [84][85][86] datasets. b The deviations of these two functionals have been recomputed with the MRCC program, [105,106] and only the MA%Ds change slightly as compared with those of Yu.…”

Section: Performances Of the Tested Methods On The Ncce31 And O23 Dsupporting

confidence: 56%

“…The methods with and without orbital optimization (OO) were extensively benchmarked with the def2‐QZVP basis set against the O23 dataset by Najibi and Goerigk . As shown in Table , the performances of the five tested methods without OO in our work are approximate to those of the well‐performed methods with and without OO as benchmarked by Najibi and Goerigk . However, the orbital‐optimized MP2.5 method outperforms the aforementioned methods with and without OO on the O23 dataset.…”

Section: Resultsmentioning

confidence: 72%

“…Therefore, the SOSEX75‐NL method seems to be relatively suitable for open‐shell noncovalent interactions. The methods with and without orbital optimization (OO) were extensively benchmarked with the def2‐QZVP basis set against the O23 dataset by Najibi and Goerigk . As shown in Table , the performances of the five tested methods without OO in our work are approximate to those of the well‐performed methods with and without OO as benchmarked by Najibi and Goerigk .…”

Section: Resultsmentioning

confidence: 74%

“…The deviations of these methods with and without OO were evaluated with the def2‐QZVP basis set, and they were taken from Najibi and Goerigk …”

Section: Resultsmentioning

confidence: 99%

“…b The deviations of these methods with and without OO were evaluated with the def2-QZVP basis set, and they were taken from Najibi and Goerigk. [123] Abbreviations: CP, counterpoise; MAD, mean absolute deviation; MD, mean deviation; RMSD, root-mean-square deviation.…”

Section: Performances Of the Tested Methods On The Ncce31 And O23 Dmentioning

confidence: 99%

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Dual‐hybrid direct random phase approximation and second‐order screened exchange with nonlocal van der Waals correlations for noncovalent interactions

Wang

2020

J Comput Chem

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We have added the nonlocal van der Waals correlation energy functional of Vydrov and Van Voorhis in 2010 (VV10NL) to the dual‐hybrid direct random phase approximation (dRPA75) and second‐order screened exchange (SOSEX75) for noncovalent interactions. The obtained methods are denoted as dRPA75‐NL and SOSEX75‐NL, and the corresponding short‐range attenuation parameters are fitted with the large aug‐cc‐pV5Z basis set against the S66 dataset. Therefore, the dRPA75‐NL method overcomes the error cancellation problem of the dRPA75 method with the relatively small aug‐cc‐pVTZ basis set for noncovalent interactions. Based on our benchmark computations, the dRPA75‐NL and SOSEX75‐NL methods perform very well on evaluating noncovalent interaction energies. Compared with the double‐hybrid density functionals (DHDFs) of DSD‐PBEP86‐NL and DOD‐PBEP86‐NL, the dRPA75‐NL and SOSEX75‐NL methods perform much better on charge transfer interactions. Furthermore, the SOSEX75‐NL method also gives insight into the development of computational methods for both closed‐shell and open‐shell noncovalent interactions. In summary, our computations demonstrate that even the full dRPA and SOSEX correlations still need additional dispersion corrections for noncovalent interactions.

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Section: Performances Of the Tested Methods On The Ncce31 And O23 Dsupporting

confidence: 56%

Section: Resultsmentioning

confidence: 72%

Section: Resultsmentioning

confidence: 74%

“…The deviations of these methods with and without OO were evaluated with the def2‐QZVP basis set, and they were taken from Najibi and Goerigk …”

Section: Resultsmentioning

confidence: 99%

Section: Performances Of the Tested Methods On The Ncce31 And O23 Dmentioning

confidence: 99%

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Dual‐hybrid direct random phase approximation and second‐order screened exchange with nonlocal van der Waals correlations for noncovalent interactions

Wang

2020

J Comput Chem

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Empirical Double‐Hybrid Density Functional Theory: A ‘Third Way’ in Between WFT and DFT

Martin

Santra

2019

Israel Journal of Chemistry

185

227

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Double hybrid density functional theory arguably sits on the seamline between wavefunction methods and DFT: it represents a special case of Rung 5 on the "Jacob's Ladder" of John P. Perdew. For large and chemically diverse benchmarks such as GMTKN55, empirical double hybrid functionals with dispersion corrections can achieve accuracies approaching wavefunction methods at a cost not greatly dissimilar to hybrid DFT approaches, provided RI-MP2 and/ or another MP2 acceleration techniques are available in the electronic structure code. Only a half-dozen or fewer empirical parameters are required. For vibrational frequencies, accuracies intermediate between CCSD and CCSD(T) can be achieved, and performance for other properties is encouraging as well. Organometallic reactions can likewise be treated well, provided static correlation is not too strong. Further prospects are discussed, including range-separated and RPA-based approaches.These are not the final page numbers! �� quantum Monte Carlo results [18] for uniform electron gases. The LDA XC functional only depends on the electronic density and not on any derivatives nor any other entities.Rung two corresponds to GGAs or generalized gradient approximations, in which the reduced density gradient is introduced in the XC functional. Examples are the popular BP86 [19,20] and PBE [21] functionals.Rung three consists of meta-GGAs (mGGAs), which additionally involve higher density derivatives (or the kinetic energy density, which contains similar information to the density Laplacian). TPSS [22] is a popular meta-GGA, as is the recent SCAN (strongly constrained and appropriate normed [23] ).Rungs two and three are often collectively referred to as semi-local functionals.Orbital-dependent DFT [24] covers rungs four and five: on rung four, only occupied orbital-dependency is introduced, while on rung five the unoccupied orbitals make their appearance. The most important rung four functionals are the hybrids, which can be further subdivided into four subclasses: * global hybrid GGAs, such as the popular B3LYP [25,26] and PBE0 [27] hybrids, as well as B97-1. [28] (We note that Hartree-Fock theory itself is a special case, with 100 % exact exchange and null correlation.) * global hybrid meta-GGAs, such as M06, [29] M06-2X, [29] and BMK [30] * range-separated hybrid GGAs, such as CAM-B3LYP [31] and ωB97X-V [32] * range-separated hybrid meta-GGAs, such as ωB97M-V [33] This leaves rung five, of which we will presently consider one subcase, the double hybrids. More general reviews have been published earlier; [34][35][36] the present review will focus primarily on our own work, as well as the broader context.

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Double hybrid DFT calculations with Slater type orbitals

Förster

Visscher

2020

J Comput Chem

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On a comprehensive database with 1,644 datapoints, covering several aspects of main-group as well as of transition metal chemistry, we assess the performance of 60 density functional approximations (DFA), among them 36 double hybrids (DH). All calculations are performed using a Slater type orbital (STO) basis set of triple-ζ (TZ) quality and the highly efficient pair atomic resolution of the identity approach for the exchange-and Coulomb-term of the KS matrix (PARI-K and PARI-J, respectively) and for the evaluation of the MP2 energy correction (PARI-MP2). Employing the quadratic scaling SOS-AO-PARI-MP2 algorithm, DHs based on the spin-opposite-scaled (SOS) MP2 approximation are benchmarked against a database of large molecules. We evaluate the accuracy of STO/PARI calculations for B3LYP as well as for the DH B2GP-PLYP and show that the combined basis set and PARI-error is comparable to the one obtained using the well-known def2-TZVPP Gaussian-type basis set in conjunction with global density fitting. While quadruple-ζ (QZ) calculations are currently not feasible for PARI-MP2 due to numerical issues, we show that, on the TZ level, Jacob's ladder for classifying DFAs is reproduced. However, while the best DHs are more accurate than the best hybrids, the improvements are less pronounced than the ones commonly found on the QZ level. For conformers of organic molecules and noncovalent interactions where very high accuracy is required for qualitatively correct results, DHs provide only small improvements over hybrids, while they still excel in thermochemistry, kinetics, transition metal chemistry and the description of strained organic systems. K E Y W O R D S ADF, benchmark, double-hybrid, KS-DFT, STO

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A Comprehensive Assessment of the Effectiveness of Orbital Optimization in Double-Hybrid Density Functionals in the Treatment of Thermochemistry, Kinetics, and Noncovalent Interactions

Cited by 20 publications

References 86 publications

Dual‐hybrid direct random phase approximation and second‐order screened exchange with nonlocal van der Waals correlations for noncovalent interactions

Dual‐hybrid direct random phase approximation and second‐order screened exchange with nonlocal van der Waals correlations for noncovalent interactions

Empirical Double‐Hybrid Density Functional Theory: A ‘Third Way’ in Between WFT and DFT

Double hybrid DFT calculations with Slater type orbitals

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