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dc.contributor.authorSmith, Daniel G. A.en_US
dc.contributor.authorJankowski, Piotren_US
dc.contributor.authorSlawik, Michalen_US
dc.contributor.authorWitek, Henryk A.en_US
dc.contributor.authorPatkowski, Konraden_US
dc.date.accessioned2014-12-08T15:36:44Z-
dc.date.available2014-12-08T15:36:44Z-
dc.date.issued2014-08-01en_US
dc.identifier.issn1549-9618en_US
dc.identifier.urihttp://dx.doi.org/10.1021/ct500347qen_US
dc.identifier.urihttp://hdl.handle.net/11536/25088-
dc.description.abstractWe investigated the basis set convergence of high-order coupled-cluster interaction energy contributions for 21 small weakly bound complexes. By performing CCSDT(Q) calculations in at least the aug-cc-pVTZ basis set, and CCSDT calculations in at least aug-cc-pVQZ (aug-cc-pVTZ for one system), we found the convergence to be quite slow. In particular, the 6-31G*(0.25) and 6-31G**(0.25,0.15) bases advocated by Hobza et al. (J. Chem. Theory Comput. 2013, 9, 2151; ibid. 2013, 9, 3420) are unsuitable for the post-CCSD(T) effects, with average errors for the CCSDT(Q)-CCSD(T) interaction energy contribution of about 80% for 6-31G**(0.25,0.15) and 110% for 6-31G*(0.25). Upgrading the basis set to aug-cc-pVDZ reduces the average error to about 35% and extremely demanding CCSDT(Q)/aug-cc-pVTZ calculations are necessary for further improvement in accuracy. An error cancellation between basis set incompleteness effects at the CCSDT-CCSD(T) and CCSDT(Q)-CCSDT levels occurs for most (but not all) complexes, making it unproductive to carry out CCSDT calculations in a larger basis set than the more demanding CCSDT(Q) calculations. We also found that the frozen natural orbital approximation at the CCSDT and CCSDT(Q) levels works well only if the thresholds for discarding least occupied natural orbitals are very tight (significantly tighter than the thresholds recommended for molecular correlation energies in the original work of Rolik and Kallay, J. Chem. Phys. 2011, 134, 124111), making the performance gains quite limited. The interaction energy contributions through CCSDT(Q) are both a necessity and a bottleneck in the construction of top-accuracy interaction potentials and further improvements in the efficiency of high-order coupled-cluster calculations will be of great help.en_US
dc.language.isoen_USen_US
dc.titleBasis Set Convergence of the Post-CCSD(T) Contribution to Noncovalent Interaction Energiesen_US
dc.typeArticleen_US
dc.identifier.doi10.1021/ct500347qen_US
dc.identifier.journalJOURNAL OF CHEMICAL THEORY AND COMPUTATIONen_US
dc.citation.volume10en_US
dc.citation.issue8en_US
dc.citation.spage3140en_US
dc.citation.epage3150en_US
dc.contributor.department應用化學系zh_TW
dc.contributor.department應用化學系分子科學碩博班zh_TW
dc.contributor.departmentDepartment of Applied Chemistryen_US
dc.contributor.departmentInstitute of Molecular scienceen_US
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