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dc.contributor.authorBistoni, Giovanni
dc.contributor.authorRiplinger, Christoph
dc.contributor.authorMinenkov, Yury
dc.contributor.authorCavallo, Luigi
dc.contributor.authorAuer, Alexander A.
dc.contributor.authorNeese, Frank
dc.date.accessioned2017-06-19T09:21:46Z
dc.date.available2017-06-19T09:21:46Z
dc.date.issued2017-06-12
dc.identifier.citationBistoni G, Riplinger C, Minenkov Y, Cavallo L, Auer AA, et al. (2017) Treating sub-valence correlation effects in domain based pair natural orbital coupled cluster calculations: an out-of-the-box approach. Journal of Chemical Theory and Computation. Available: http://dx.doi.org/10.1021/acs.jctc.7b00352.
dc.identifier.issn1549-9618
dc.identifier.issn1549-9626
dc.identifier.pmid28605579
dc.identifier.doi10.1021/acs.jctc.7b00352
dc.identifier.urihttp://hdl.handle.net/10754/625068
dc.description.abstractThe validity of the main approximations used in canonical and domain based pair natural orbital coupled cluster methods (CCSD(T) and DLPNO-CCSD(T), respectively) in standard chemical applications is discussed. In particular, we investigate the dependence of the results on the number of electrons included in the correlation treatment in frozen-core (FC) calculations and on the main threshold governing the accuracy of DLPNO all-electron (AE) calculations. Initially, scalar relativistic orbital energies for the ground state of the atoms from Li to Rn in the periodic table are calculated. An energy criterion is applied for determining the orbitals that can be excluded from the correlation treatment in FC coupled cluster calculations without significant loss of accuracy. The heterolytic dissociation energy (HDE) of a series of metal compounds (LiF, NaF, AlF3, CaF2, CuF, GaF3, YF3, AgF, InF3, HfF4 and AuF) is calculated at the canonical CCSD(T) level, and the dependence of the results on the number of correlated electrons is investigated. Although for many of the studied reactions sub-valence correlation effects contribute significantly to the HDE, the use of an energy criterion permits a conservative definition of the size of the core, allowing FC calculations to be performed in a black-box fashion while retaining chemical accuracy. A comparison of the CCSD and the DLPNO-CCSD methods in describing the core-core, core-valence and valence-valence components of the correlation energy is given. It is found that more conservative thresholds must be used for electron pairs containing at least one core electron in order to achieve high accuracy in AE DLPNO-CCSD calculations relative to FC calculations. With the new settings, the DLPNO-CCSD method reproduces canonical CCSD results in both AE and FC calculations with the same accuracy.
dc.description.sponsorshipGiovanni Bistoni, Alexander A. Auer and Frank Neese gratefully acknowledge the Priority Program ’’Control of London Dispersion Interactions in Molecular Chemistry’’ (SPP 1807) of the DFG for financial support. Yury Minenkov and Luigi Cavallo gratefully acknowledge the financial support from King Abdullah University of Science and Technology (KAUST).
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.jctc.7b00352
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Theory and Computation, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.jctc.7b00352.
dc.titleTreating sub-valence correlation effects in domain based pair natural orbital coupled cluster calculations: an out-of-the-box approach
dc.typeArticle
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Division
dc.identifier.journalJournal of Chemical Theory and Computation
dc.eprint.versionPost-print
dc.contributor.institutionDepartment of Molecular Theory and Spectroscopy, Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34-36, D-45470 Mülheim an der Ruhr, Germany.
kaust.personMinenkov, Yury
kaust.personCavallo, Luigi
refterms.dateFOA2018-06-12T00:00:00Z


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