Monte Carlo configuration interaction with perturbation corrections for dissociation energies of first row diatomic molecules: C-2, N-2, O-2, CO, and NO

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dc.contributor.authorKelly, Thomas P.
dc.contributor.authorPerera, Ajith
dc.contributor.authorBartlett, Rodney J.
dc.contributor.authorGreer, James C.
dc.date.accessioned2017-01-20T14:48:43Z
dc.date.available2017-01-20T14:48:43Z
dc.date.issued2014-02-28
dc.date.updated2017-01-17T21:06:40Z
dc.description.abstractDissociation energies for the diatomic molecules C2, N2, O2, CO, and NO are estimated using the Monte Carlo configuration interaction (MCCI) and augmented by a second order perturbation theory correction. The calculations are performed using the correlation consistent polarized valence “triple zeta” atomic orbital basis and resulting dissociation energies are compared to coupled cluster calculations including up to triple excitations (CCSDT) and Full Configuration Interaction Quantum Monte Carlo (FCIQMC) estimates. It is found that the MCCI method readily describes the correct behavior for dissociation for the diatomics even when capturing only a relatively small fraction (∼80%) of the correlation energy. At this level only a small number of configurations, typically O(103) from a FCI space of dimension O(1014), are required to describe dissociation. Including the perturbation correction to the MCCI estimates, the difference in dissociation energies with respect to CCSDT ranges between 1.2 and 3.1 kcal/mol, and the difference when comparing to FCIQMC estimates narrows to between 0.5 and 1.9 kcal/mol. Discussions on MCCI's ability to recover static and dynamic correlations and on the form of correlations in the electronic configuration space are presented.en
dc.description.statusPeer revieweden
dc.description.versionPublished Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.articleid084114
dc.identifier.citationKelly, T. P., Perera, A., Bartlett, R. J. and Greer, J. C. (2014) 'Monte Carlo configuration interaction with perturbation corrections for dissociation energies of first row diatomic molecules: C2, N2, O2, CO, and NO', The Journal of Chemical Physics, 140(8), pp. 084114. doi:10.1063/1.4866609en
dc.identifier.doi10.1063/1.4866609
dc.identifier.endpage084114-10en
dc.identifier.issn0021-9606
dc.identifier.issued8en
dc.identifier.journaltitleThe Journal of Chemical Physicsen
dc.identifier.startpage084114-1en
dc.identifier.urihttps://hdl.handle.net/10468/3490
dc.identifier.volume140en
dc.language.isoenen
dc.publisherAIP Publishingen
dc.rights© 2014, AIP Publishing. This 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 J. Chem. Phys. 140, 084114 (2014); and may be found at http://dx.doi.org/10.1063/1.4866609en
dc.subjectMatrix renormalization-groupen
dc.subjectQuantum-chemistryen
dc.subjectBenchmarken
dc.subjectSelectionen
dc.subjectAtomsen
dc.titleMonte Carlo configuration interaction with perturbation corrections for dissociation energies of first row diatomic molecules: C-2, N-2, O-2, CO, and NOen
dc.typeArticle (peer-reviewed)en
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