Cholesky-decomposed densities in Laplace-based second-order Møller–Plesset perturbation theory

Zienau, Jan; Clin, Lucien; Doser, Bernd; Ochsenfeld, Christian

doi:10.1063/1.3142592

Cited by 53 publications

(51 citation statements)

References 29 publications

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“…For larger molecules, an efficient cubicscaling MP2 method has been implemented in Q-CHEM. The method is grounded on the atomic orbital-based MP2 formulation and uses a Cholesky decomposition of pseudodensity matrices (CDD) [147,148] in combination with integral screening procedures using QQR integral estimates [148][149][150]. Using the RI approach and efficient sparse matrix algebra, the RI-CDD-MP2 method shows a fairly small prefactor for a reduced-scaling method.…”

Section: Perturbative Methodsmentioning

confidence: 99%

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

Shao¹,

Gan²,

Epifanovsky³

et al. 2014

Molecular Physics

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2,709

2,077

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A summary of the technical advances that are incorporated in the fourth major release of the Q-Chem quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and openshell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Møller-Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Some specific chemical examples include calculations on the strongly correlated Cr 2 dimer, exploring zeolitecatalysed ethane dehydrogenation, energy decomposition analysis of a charged ter-molecular complex arising from glycerol photoionisation, and natural transition orbitals for a Frenkel exciton state in a nine-unit model of a self-assembling nanotube.Keywords quantum chemistry, software, electronic structure theory, density functional theory, electron correlation, computational modelling, Q-Chem Disciplines Chemistry CommentsThis article is from Molecular Physics: An International Journal at the Interface Between Chemistry and Physics 113 (2015): 184, doi:10.1080/00268976.2014. RightsWorks produced by employees of the U.S. Government as part of their official duties are not copyrighted within the U.S. The content of this document is not copyrighted. Authors 185A summary of the technical advances that are incorporated in the fourth major release of the Q-CHEM quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and open-shell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Møller-Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Some specific chemical examples include calculations on the strongly corre...

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Section: Perturbative Methodsmentioning

confidence: 99%

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

Shao¹,

Gan²,

Epifanovsky³

et al. 2014

Molecular Physics

Self Cite

2,709

2,077

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“…28,29 Recent promising developments in this field include the pair natural orbital (PNO) CC methods of Neese and co-workers, [30][31][32][33] the orbital-specific virtual (OSV) approximation of Chan, Manby, and co-workers, [34][35][36][37] as well as the general sparse tensor frameworks by Parkhill and Head-Gordon 38 and Kats and Manby,39 which can facilitate the implementation of local correlation methods. We should also mention the related linear-scaling MP2 approaches of Ochsenfeld et al 40,41 and VandeVondele and co-workers, 42 which allow for impressive MP2 calculations for large molecules.…”

Section: Introductionmentioning

confidence: 99%

An efficient linear-scaling CCSD(T) method based on local natural orbitals

Rolik

Szegedy

Ladjánszki

et al. 2013

The Journal of Chemical Physics

353

318

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An improved version of our general-order local coupled-cluster (CC) approach [Z. Rolik and M. Kállay, J. Chem. Phys. 135, 104111 (2011)] and its efficient implementation at the CC singles and doubles with perturbative triples [CCSD(T)] level is presented. The method combines the cluster-in-molecule approach of Li and co-workers [J. Chem. Phys. 131, 114109 (2009)] with frozen natural orbital (NO) techniques. To break down the unfavorable fifth-power scaling of our original approach a two-level domain construction algorithm has been developed. First, an extended domain of localized molecular orbitals (LMOs) is assembled based on the spatial distance of the orbitals. The necessary integrals are evaluated and transformed in these domains invoking the density fitting approximation. In the second step, for each occupied LMO of the extended domain a local subspace of occupied and virtual orbitals is constructed including approximate second-order Mo̸ller-Plesset NOs. The CC equations are solved and the perturbative corrections are calculated in the local subspace for each occupied LMO using a highly-efficient CCSD(T) code, which was optimized for the typical sizes of the local subspaces. The total correlation energy is evaluated as the sum of the individual contributions. The computation time of our approach scales linearly with the system size, while its memory and disk space requirements are independent thereof. Test calculations demonstrate that currently our method is one of the most efficient local CCSD(T) approaches and can be routinely applied to molecules of up to 100 atoms with reasonable basis sets.

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“…However, the development of new computational algorithms like density fitting [10][11][12][13][14][15][16][17][18] and Cholesky decomposition [19][20][21][22][23][24] (see also Refs. 25 and 26 for singular value decomposition approaches in coupled-cluster theory), the transformation into local basis functions, 14,15,[27][28][29][30][31][32][33][34][35][36][37][38] or the exploitation of parallel computer architectures 18,[39][40][41][42] has lead to an increase of the feasibility of standard ab initio methods also for extended molecular systems so that electron correlation effects can nowadays also accurately be accounted for quite large systems that formally could be described only on the density functional theory level.…”

Section: Introductionmentioning

confidence: 99%

Third-order corrections to random-phase approximation correlation energies

Heßelmann

2011

The Journal of Chemical Physics

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Several random-phase approximation (RPA) correlation methods were compared in third order of perturbation theory. While all of the considered approaches are exact in second order of perturbation theory, it is found that their corresponding third-order correlation energy contributions strongly differ from the exact third-order correlation energy contribution due to missing interactions of the particle-particle−hole-hole type. Thus a simple correction method is derived which makes the different RPA methods also exact to third-order of perturbation theory. By studying the reaction energies of 16 chemical reactions for 21 small organic molecules and intermolecular interaction energies of 23 intermolecular complexes comprising weakly bound and hydrogen-bridged systems, it is found that the third-order correlation energy correction considerably improves the accuracy of RPA methods if compared to coupled-cluster singles doubles with perturbative triples as a reference.

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Cholesky-decomposed densities in Laplace-based second-order Møller–Plesset perturbation theory

Cited by 53 publications

References 29 publications

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

An efficient linear-scaling CCSD(T) method based on local natural orbitals

Third-order corrections to random-phase approximation correlation energies

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