Short range DFT combined with long-range local RPA within a range-separated hybrid DFT framework

Chermak, Edrisse; Mussard, Bastien; Ángyán, János G.; Reinhardt, Peter

doi:10.1016/j.cplett.2012.08.073

Cited by 30 publications

(15 citation statements)

References 45 publications

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“…10) which allows one to combine a short-range density-functional approximation with a long-range RPA-type approximation. [11][12][13][14][15][16][17][18][19][20] As a result of the increasing interest in RPA, there are now several RPA formulations in which RPA equations can be derived, namely the adiabatic connection, 7,21,22 dielectric matrix, [23][24][25] plasmon 26,27 formula and ring coupled-cluster doubles 16,27,28 formulations. Moreover, within these formulations, many variants of RPA (e.g., direct RPA, 27 RPA with exact Hartree-Fock (HF) exchange, [28][29][30] RPA with exact KohnSham exchange 31 ) can be defined (see also Refs.…”

Section: Introductionmentioning

confidence: 99%

Spin-unrestricted random-phase approximation with range separation: Benchmark on atomization energies and reaction barrier heights

Mussard

Reinhardt

Ángyán

et al. 2015

The Journal of Chemical Physics

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We consider several spin-unrestricted random-phase approximation (RPA) variants for calculating correlation energies, with and without range separation, and test them on datasets of atomization energies and reaction barrier heights. We show that range separation greatly improves the accuracy of all RPA variants for these properties. Moreover, we show that a RPA variant with exchange, hereafter referred to as RPAx-SO2, first proposed by Szabo and Ostlund [A. Szabo and N. S. Ostlund, J. Chem. Phys. 67, 4351 (1977)] in a spin-restricted closed-shell formalism, and extended here to a spin-unrestricted formalism, provides on average the most accurate range-separated RPA variant for atomization energies and reaction barrier heights. Since this range-separated RPAx-SO2 method had already been shown to be among the most accurate range-separated RPA variants for weak intermolecular interactions [J. Toulouse, W. Zhu, A. Savin, G. Jansen, and J. G. Ángyán, J. Chem. Phys. 135, 084119 (2011)], this works confirms range-separated RPAx-SO2 as a promising method for general chemical applications.

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Section: Introductionmentioning

confidence: 99%

Spin-unrestricted random-phase approximation with range separation: Benchmark on atomization energies and reaction barrier heights

Mussard

Reinhardt

Ángyán

et al. 2015

The Journal of Chemical Physics

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“…Significant effort was spent in the past decade to develop methods that strike a reasonable compromise between accuracy and computational cost for dispersion-dominated interactions. 11 Some examples are empirical scaling of different contributions in wavefunction-based methods, 12,13,14,15 parametrizing exchange-correlation functionals to account for dispersion, 16 combining short-range DFT correlation with long-range MP2 (MP2C) 17 or RPA 18 and adding explicit dispersion terms to conventional DFT. 19 Other promising approaches are local electron correlation theories, 20 Symmetry-Adapted Perturbation Theory 21 based on DFT 22,23 , modification of the core potentials to mimic dispersion, 24,25 and methods aiming at incorporating the physics of dispersion in DFT.…”

Section: Introductionmentioning

confidence: 99%

Accuracy of Quantum Chemical Methods for Large Noncovalent Complexes

Sedlák

Janowski

Pitoňák

et al. 2013

J. Chem. Theory Comput.

321

411

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We evaluate the performance of the most widely used wavefunction, density functional theory, and semiempirical methods for the description of noncovalent interactions in a set of larger, mostly dispersion-stabilized noncovalent complexes (the L7 data set). The methods tested include MP2, MP3, SCS-MP2, SCS(MI)-MP2, MP2.5, MP2.X, MP2C, DFT-D, DFT-D3 (B3-LYP-D3, B-LYP-D3, TPSS-D3, PW6B95-D3, M06-2X-D3) and M06-2X, and semiempirical methods augmented with dispersion and hydrogen bonding corrections: SCC-DFTB-D, PM6-D, PM6-DH2 and PM6-D3H4. The test complexes are the octadecane dimer, the guanine trimer, the circumcoronene…adenine dimer, the coronene dimer, the guanine-cytosine dimer, the circumcoronene…guanine-cytosine dimer, and an amyloid fragment trimer containing phenylalanine residues. The best performing method is MP2.5 with relative root mean square deviation (rRMSD) of 4 %. It can thus be recommended as an alternative to the CCSD(T)/CBS (alternatively QCISD(T)/CBS) benchmark for molecular systems which exceed current computational capacity. The second best non-DFT method is MP2C with rRMSD of 8 %. A method with the most favorable “accuracy/cost” ratio belongs to the DFT family: BLYP-D3, with an rRMSD of 8 %. Semiempirical methods deliver less accurate results (the rRMSD exceeds 25 %). Nevertheless, their absolute errors are close to some much more expensive methods such as M06-2X, MP2 or SCS(MI)-MP2, and thus their price/performance ratio is excellent.

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“…The strategy of range-separated DFT consists in separating the Coulomb electron-electron interaction into long-range and shortrange components, and treating the long-range part by an explicit many-body wave-function method and the short-range part by a density-functional approximation. In particular, for describing systems with van der Waals dispersion interactions, it is appropriate to use methods based on many-body perturbation theory for the longrange part such as second-order perturbation theory [4][5][6][7][8][9][10][11][12][13][14][15][16], coupled-cluster theory [17][18][19][20][21], or random-phase approximations [22][23][24][25][26][27][28][29][30][31][32][33][34].…”

Section: Introductionmentioning

confidence: 99%

Basis convergence of range-separated density-functional theory

Franck

Mussard

Luppi

et al. 2015

The Journal of Chemical Physics

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Range-separated density-functional theory is an alternative approach to Kohn-Sham densityfunctional theory. The strategy of range-separated density-functional theory consists in separating the Coulomb electron-electron interaction into long-range and short-range components, and treating the long-range part by an explicit many-body wave-function method and the short-range part by a density-functional approximation. Among the advantages of using many-body methods for the long-range part of the electron-electron interaction is that they are much less sensitive to the oneelectron atomic basis compared to the case of the standard Coulomb interaction. Here, we provide a detailed study of the basis convergence of range-separated density-functional theory. We study the convergence of the partial-wave expansion of the long-range wave function near the electron-electron coalescence. We show that the rate of convergence is exponential with respect to the maximal angular momentum L for the long-range wave function, whereas it is polynomial for the case of the Coulomb interaction. We also study the convergence of the long-range second-order Møller-Plesset correlation energy of four systems (He, Ne, N2, and H2O) with the cardinal number X of the Dunning basis sets cc-p(C)VXZ, and find that the error in the correlation energy is best fitted by an exponential in X. This leads us to propose a three-point complete-basis-set extrapolation scheme for range-separated density-functional theory based on an exponential formula.

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Short range DFT combined with long-range local RPA within a range-separated hybrid DFT framework

Cited by 30 publications

References 45 publications

Spin-unrestricted random-phase approximation with range separation: Benchmark on atomization energies and reaction barrier heights

Spin-unrestricted random-phase approximation with range separation: Benchmark on atomization energies and reaction barrier heights

Accuracy of Quantum Chemical Methods for Large Noncovalent Complexes

Basis convergence of range-separated density-functional theory

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