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dc.contributor.authorGuo, Yang
dc.contributor.authorRiplinger, Christoph
dc.contributor.authorBecker, Ute
dc.contributor.authorLiakos, Dimitrios G.
dc.contributor.authorMinenkov, Yury
dc.contributor.authorCavallo, Luigi
dc.contributor.authorNeese, Frank
dc.date.accessioned2018-01-28T07:01:35Z
dc.date.available2018-01-28T07:01:35Z
dc.date.issued2018-01-04
dc.identifier.citationGuo Y, Riplinger C, Becker U, Liakos DG, Minenkov Y, et al. (2018) Communication: An improved linear scaling perturbative triples correction for the domain based local pair-natural orbital based singles and doubles coupled cluster method [DLPNO-CCSD(T)]. The Journal of Chemical Physics 148: 011101. Available: http://dx.doi.org/10.1063/1.5011798.
dc.identifier.issn0021-9606
dc.identifier.issn1089-7690
dc.identifier.pmid29306283
dc.identifier.doi10.1063/1.5011798
dc.identifier.urihttp://hdl.handle.net/10754/626850
dc.description.abstractIn this communication, an improved perturbative triples correction (T) algorithm for domain based local pair-natural orbital singles and doubles coupled cluster (DLPNO-CCSD) theory is reported. In our previous implementation, the semi-canonical approximation was used and linear scaling was achieved for both the DLPNO-CCSD and (T) parts of the calculation. In this work, we refer to this previous method as DLPNO-CCSD(T0) to emphasize the semi-canonical approximation. It is well-established that the DLPNO-CCSD method can predict very accurate absolute and relative energies with respect to the parent canonical CCSD method. However, the (T0) approximation may introduce significant errors in absolute energies as the triples correction grows up in magnitude. In the majority of cases, the relative energies from (T0) are as accurate as the canonical (T) results of themselves. Unfortunately, in rare cases and in particular for small gap systems, the (T0) approximation breaks down and relative energies show large deviations from the parent canonical CCSD(T) results. To address this problem, an iterative (T) algorithm based on the previous DLPNO-CCSD(T0) algorithm has been implemented [abbreviated here as DLPNO-CCSD(T)]. Using triples natural orbitals to represent the virtual spaces for triples amplitudes, storage bottlenecks are avoided. Various carefully designed approximations ease the computational burden such that overall, the increase in the DLPNO-(T) calculation time over DLPNO-(T0) only amounts to a factor of about two (depending on the basis set). Benchmark calculations for the GMTKN30 database show that compared to DLPNO-CCSD(T0), the errors in absolute energies are greatly reduced and relative energies are moderately improved. The particularly problematic case of cumulene chains of increasing lengths is also successfully addressed by DLPNO-CCSD(T).
dc.description.sponsorshipF.N. and Y.G. gratefully acknowledge financial support by the Max Planck Society and the cluster of excellence (RESOLV, University of Bochum, No. EXC 1069). Y.G. is thankful to Peter Pinski for helpful discussion.
dc.publisherAIP Publishing
dc.relation.urlhttp://aip.scitation.org/doi/10.1063/1.5011798
dc.rightsThis article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. The following article appeared in The Journal of Chemical Physics and may be found at http://doi.org/10.1063/1.5011798.
dc.subjectCoupled cluster
dc.subjectBasis sets
dc.subjectElectron correlation calculations
dc.subjectOrganic compounds
dc.subjectInverse problems
dc.titleCommunication: An improved linear scaling perturbative triples correction for the domain based local pair-natural orbital based singles and doubles coupled cluster method [DLPNO-CCSD(T)]
dc.typeArticle
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Division
dc.contributor.departmentChemical Science Program
dc.identifier.journalThe Journal of Chemical Physics
dc.eprint.versionPublisher's Version/PDF
dc.contributor.institutionMax Planck Institut für Chemische Energiekonversion, Stiftstr. 34-36, D-45470 Mülheim an der Ruhr, Germany
kaust.personMinenkov, Yury
kaust.personCavallo, Luigi
dc.date.published-online2018-01-04
dc.date.published-print2018-01-07


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