Seniority zero pair coupled cluster doubles theory

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2014
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AIP Publishing
Abstract

Coupled clusterᅠtheoryᅠwith single and doubleᅠexcitationsᅠaccurately describes weak electronᅠcorrelationᅠbut is known to fail in cases of strong staticᅠcorrelation.ᅠFascinatingly, however, pairᅠcoupled clusterᅠdoubles (p-CCD), a simplified version of theᅠtheoryᅠlimited to pairᅠexcitationsᅠthat preserve the seniority of the reference determinant (i.e.,ᅠthe number of unpaired electrons), hasᅠmean fieldᅠcomputational cost and is an excellent approximation to the full configuration interaction (FCI) of the paired space provided that the orbital basis defining the pairing scheme is adequately optimized. In previous work, we have shown that optimization of the pairing scheme in the seniority zero FCI leads to a very accurate description of staticᅠcorrelation.ᅠThe same conclusion extends to p-CCD if the orbitals are optimized to make the p-CCD energy stationary. We here demonstrate these results with numerous examples. We also explore the contributions of different seniority sectors to theᅠcoupled clusterᅠdoublesᅠ(CCD)ᅠcorrelationᅠenergy using different orbital bases. We consider both Hartree-Fock and Brueckner orbitals, and the role of orbital localization. We show how one can pair the orbitals so that the role of the Brueckner orbitals at theᅠCCDᅠlevel is retained at the p-CCD level. Moreover, we explore ways of extendingᅠCCDᅠto accurately describe strongly correlated systems.

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Stein, Tamar, Henderson, Thomas M. and Scuseria, Gustavo E.. "Seniority zero pair coupled cluster doubles theory." The Journal of Chemical Physics, 140, no. 21 (2014) AIP Publishing: http://dx.doi.org/10.1063/1.4880819.

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