The orbital-specific-virtual local coupled cluster singles and doubles method

Yang, Jun; Chan, Garnet Kin‐Lic; Manby, Frederick R.; Schütz, Martin; Werner, Hans‐Joachim

doi:10.1063/1.3696963

Cited by 185 publications

(184 citation statements)

References 77 publications

(144 reference statements)

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“…139 The domain-size problem can be largely alleviated using Meyer's pair natural orbitals (PNOs), 140 as revived by Neese et al, 141 because the accuracy can be controlled a priori by a single occupation number threshold for the truncation of PNOs. The steep scalings needed to generate PNOs can be avoided using local variants that employ intermediates with PAO domains or the orbital-specific virtuals (OSVs) 142 often generated from extended PAO domains to attain asymptotic linear scalings. 135,143,144 Among the choices of virtual orbitals, PNOs provide the most compact representation of domains with high accuracy.…”

Section: Large Moleculesmentioning

confidence: 99%

Perspective: Explicitly correlated electronic structure theory for complex systems

Grüneis

Hirata

Ohnishi

et al. 2017

The Journal of Chemical Physics

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The explicitly correlated approach is one of the most important breakthroughs in ab initio electronic structure theory, providing arguably the most compact, accurate, and efficient ansatz for describing the correlated motion of electrons. Since Hylleraas first used an explicitly correlated wave function for the He atom in 1929, numerous attempts have been made to tackle the significant challenges involved in constructing practical explicitly correlated methods that are applicable to larger systems. These include identifying suitable mathematical forms of a correlated wave function and an efficient evaluation of many-electron integrals. R12 theory, which employs the resolution of the identity approximation, emerged in 1985, followed by the introduction of novel correlation factors and wave function ansätze, leading to the establishment of F12 theory in the 2000s. Rapid progress in recent years has significantly extended the application range of explicitly correlated theory, offering the potential of an accurate wave-function treatment of complex systems such as photosystems and semiconductors. This perspective surveys explicitly correlated electronic structure theory, with an emphasis on recent stochastic and deterministic approaches that hold significant promise for applications to large and complex systems including solids. Published by AIP Publishing. [http://dx

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Section: Large Moleculesmentioning

confidence: 99%

Perspective: Explicitly correlated electronic structure theory for complex systems

Grüneis

Hirata

Ohnishi

et al. 2017

The Journal of Chemical Physics

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“…We note in passing, that for local CCSD(T) calculations a simple incremental correction at the MP2 level fixes the basis set truncation as well as the domain error, yielding CCSD(T) results close to the basis set limit. 48,49 The finite clusters utilized to mimic the intralayer argonargon, and the interlayer-slab argon-MgO interactions are the equilateral argon trimer, and the Ar-Na 2 Mg 3 O 4 dimer (depicted in Appendix B), respectively. In the latter, the MgO-part is a quadratic planar cut from the periodic slab with two sodium atoms (yet with Mg basis set) substituting the border Mg atoms to preserve charge neutrality.…”

Section: B Finite Cluster Calculations and Correction Scheme For Permentioning

confidence: 99%

Geometrical frustration of an argon monolayer adsorbed on the MgO (100) surface: An accurate periodicab initiostudy

et al. 2012

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We present an accurate first-principles method for calculating the energy of physisorption, based on a fully periodic local Møller-Plesset second order perturbation theory (LMP2) treatment. The LMP2 inter-surfaceadsorbate interaction energy is scaled with a factor, obtained by comparing the method error of LMP2 versus coupled cluster singles doubles theory with perturbative triples at the basis set limit in small clusters mimicking the system under study. This method is applied to the investigation of geometrical frustration in argon monolayers adsorbed on the MgO (100) surface. It is found that several arrangements of the argon monolayer, i.e., 3 × 2, 4 × 2, optimal hexagonal, and ζ × 2 1D noncommensurate have very similar adsorption energies, which agrees with the experimental observations. Moreover, this study provides further insight in to the Ar-MgO adsorption process and sheds light on a controversy among different experiments. The calculated adsorption energy of 2.3 kcal/mol is in a very good agreement with the experimental values, which range from 2.0 to 2.3 kcal/mol, and provides a new benchmark for this system.

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“…41 Recently, we presented an efficient implementation of OSV-local coupled cluster theory with singles and doubles (LCCSD). 39 In the present work, we extend the method to OSV-LCCSD(T). To this end, we adapt our previous PAO based triples program [42][43][44] according to the OSV-L(T) formalism.…”

Section: Introductionmentioning

confidence: 99%

“…Obvious examples are the Cholesky [10][11][12][13][14] and singular value decompositions, 15 and density fitting. [16][17][18][19][20][21][22] Also schemes defining new occupied and virtual orbital sets, such as the projected atomic orbital (PAO) based local correlation, [23][24][25][26][27] the pair natural orbital (PNO), [28][29][30][31][32][33][34][35][36][37] and the orbital specific virtual (OSV) 38,39 methods can be interpreted as tensor factorizations. All these methods substitute the delocalized occupied Hartree-Fock orbitals by (still mutually orthogonal) localized molecular orbitals (LMOs), obtained by a unitary transformation of the former.…”

Section: Introductionmentioning

confidence: 99%

The orbital-specific virtual local triples correction: OSV-L(T)

Schütz

Yang

Chan

et al. 2013

The Journal of Chemical Physics

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101

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A local method based on orbital specific virtuals (OSVs) for calculating the perturbative triples correction in local coupled cluster calculations is presented. In contrast to the previous approach based on projected atomic orbitals (PAOs), described by Schütz [J. Chem. Phys. 113, 9986 (2000)], the new scheme works without any ad hoc truncations of the virtual space to domains. A single threshold defines the pair and triple specific virtual spaces completely and automatically. It is demonstrated that the computational cost of the method scales linearly with molecular size. Employing the recommended threshold a similar fraction of the correlation energy is recovered as with the original PAO method at a somewhat lower cost. A benchmark for 52 reactions demonstrates that for reaction energies the intrinsic accuracy of the coupled cluster with singles and doubles excitations and a perturbative treatment of triples excitations method can be reached by OSV-local coupled cluster theory with singles and doubles and perturbative triples, provided a MP2 correction is applied that accounts for basis set incompleteness errors as well as for remaining domain errors. As an application example the interaction energies of the guanine-cytosine dimers in the Watson-Crick and stacked arrangements are investigated at the level of local coupled cluster theory with singles and doubles and perturbative triples. Based on these calculations we propose new complete-basis-set-limit estimates for these interaction energies at this level of theory.

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The orbital-specific-virtual local coupled cluster singles and doubles method

Cited by 185 publications

References 77 publications

Perspective: Explicitly correlated electronic structure theory for complex systems

Perspective: Explicitly correlated electronic structure theory for complex systems

Geometrical frustration of an argon monolayer adsorbed on the MgO (100) surface: An accurate periodicab initiostudy

The orbital-specific virtual local triples correction: OSV-L(T)

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