Explicit correlation and basis set superposition error: The structure and energy of carbon dioxide dimer

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dc.contributor.authorMcMahon, Jordan D.
dc.contributor.authorLane, Joseph R.
dc.date.accessioned2012-07-13T01:00:14Z
dc.date.available2012-07-13T01:00:14Z
dc.date.copyright2011
dc.date.issued2011
dc.description.abstractWe have investigated the slipped parallel and t-shaped structures of carbon dioxide dimer [(CO₂)₂] using both conventional and explicitly correlated coupled cluster methods, inclusive and exclusive of counterpoise (CP) correction. We have determined the geometry of both structures with conventional coupled cluster singles doubles and perturbative triples theory [CCSD(T)] and explicitly correlated cluster singles doubles and perturbative triples theory [CCSD(T)-F12b] at the complete basis set (CBS) limits using custom optimization routines. Consistent with previous investigations, we find that the slipped parallel structure corresponds to the global minimum and is 1.09 kJ mol⁻¹ lower in energy. For a given cardinal number, the optimized geometries and interaction energies of (CO₂)₂ obtained with the explicitly correlated CCSD(T)-F12b method are closer to the CBS limit than the corresponding conventional CCSD(T) results. Furthermore, the magnitude of basis set superposition error (BSSE) in the CCSD(T)-F12b optimized geometries and interaction energies is appreciably smaller than the magnitude of BSSE in the conventional CCSD(T) results. We decompose the CCSD(T) and CCSD(T)-F12b interaction energies into the constituent HF or HF CABS, CCSD or CCSD-F12b, and (T) contributions. We find that the complementary auxiliary basis set (CABS) singles correction and the F12b approximation significantly reduce the magnitude of BSSE at the HF and CCSD levels of theory, respectively. For a given cardinal number, we find that non-CP corrected, unscaled triples CCSD(T)-F12b/VXZ-F12 interaction energies are in overall best agreement with the CBS limit.en_NZ
dc.format.mimetypeapplication/pdf
dc.identifier.citationMcMahon, J.D. & Lane, J.R. (2011). Explicit correlation and basis set superposition error: The structure and energy of carbon dioxide dimer. The Journal of Chemical Physics, 135, 154309.en_NZ
dc.identifier.doi10.1063/1.3653230en_NZ
dc.identifier.urihttps://hdl.handle.net/10289/6458
dc.language.isoen
dc.publisherAmerican Institute of Physicsen_NZ
dc.relation.isPartOfJournal of Chemical Physicsen_NZ
dc.relation.ispartofThe Journal of Chemical Physics
dc.relation.urihttp://jcp.aip.org/resource/1/jcpsa6/v135/i15/p154309_s1en_NZ
dc.rightsThis article has been published in the journal: The Journal of Chemical Physics. © 2011 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.en_NZ
dc.subjectchemistryen_NZ
dc.subjectcarbon compoundsen_NZ
dc.subjectcoupled cluster calculationsen_NZ
dc.subjectHF calculationsen_NZ
dc.subjectmolecular configurationsen_NZ
dc.titleExplicit correlation and basis set superposition error: The structure and energy of carbon dioxide dimeren_NZ
dc.typeJournal Articleen_NZ
pubs.begin-page154309en_NZ
pubs.elements-id37128
pubs.end-page154309en_NZ
pubs.issue15en_NZ
pubs.volume135en_NZ
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