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dc.contributor.authorLane, Joseph R.
dc.contributor.authorKjaergaard, Henrik G.
dc.date.accessioned2010-05-19T23:09:45Z
dc.date.available2010-05-19T23:09:45Z
dc.date.issued2010
dc.identifier.citationLane, J.R. & Kjaergaard, H.G. (2010). XH-stretching overtone transitions calculated using explicitly correlated coupled cluster methods. The Journal of Chemical Physics, 132, 174304.en
dc.identifier.urihttps://hdl.handle.net/10289/3888
dc.description.abstractWe have calculated XH-stretching (where X=O, C, F, Cl) fundamental and overtone transitions for three diatomics and a few small molecules using a local mode model. The potential energy curves and dipole moment functions are calculated using the recently developed explicitly correlated coupled cluster with single doubles and perturbative triples theory [CCSD_T_-F12] with the associated VXZ-F12 (where X=D, T, Q) basis sets. We find that the basis set convergence of calculated frequencies and oscillator strengths obtained with the explicitly correlated method is much more rapid than with conventional CCSD(T) and the Dunning type correlation consistent basis sets. Furthermore, CCSD(T)-F12 frequencies and oscillator strengths obtained with the VTZ-F12 and VQZ-F12 basis sets are found to be in excellent agreement with the CCSD(T) complete basis set limit. We find that comparison of CCSD(T)-F12 frequencies with experiment is less good. The inclusion of explicit correlation exposes the inherent error of the CCSD(T) method to overestimate vibrational frequencies, which is normally compensated by basis set incompleteness error. As a consequence, we suggest that conventional CCSD(T) in combination with the aug-cc-pVTZ or aug-cc-pVQZ basis sets is likely to yield calculated XH-stretching frequencies in closest agreement with experiment.en
dc.format.mimetypeapplication/pdf
dc.language.isoen
dc.publisherAmerican Institute of Physicsen_NZ
dc.relation.urihttp://jcp.aip.org/jcpsa6/v132/i17/p174304_s1en
dc.rightsThis article has been published in the journal: The Journal of Chemical Physics. © 2010 American Institute of Physics.en
dc.subjectXH-stretchingen
dc.subjectcoupled cluster calculationsen
dc.subjecthydrogen compoundsen
dc.subjectmolecular momentsen
dc.subjectorganic compoundsen
dc.subjectoscillator strengthsen
dc.subjectperturbation theoryen
dc.subjectpotential energy surfacesen
dc.subjectvibrational statesen
dc.subjectwateren
dc.titleXH-stretching overtone transitions calculated using explicitly correlated coupled cluster methodsen
dc.typeJournal Articleen
dc.identifier.doi10.1063/1.3408192en
dc.relation.isPartOfThe Journal of Chemical Physicsen_NZ
pubs.begin-page1en_NZ
pubs.elements-id34900
pubs.end-page11en_NZ
pubs.issue17en_NZ
pubs.volume132en_NZ


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