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    Seniority number description of potential energy surfaces: Symmetric dissociation of water, N2, C2, and Be2

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    Author
    Bytautas, Laimutis; Scuseria, Gustavo E.; Ruedenberg, Klaus
    Date
    2015
    Abstract
    The present study further explores the concept of the seniority number (Ω) by examining different configuration interaction (CI) truncation strategies in generating compact wave functions in a systematic way. While the role of Ω in addressing static (strong) correlation problem has been addressed in numerous previous studies, the usefulness of seniority number in describing weak (dynamic) correlation has not been investigated in a systematic way. Thus, the overall objective in the present work is to investigate the role of Ω in addressing also dynamic electron correlation in addition to the static correlation. Two systematic CI truncation strategies are compared beyond minimal basis sets and full valence active spaces. One approach is based on the seniority number (defined as the total number of singly occupied orbitals in a determinant) and another is based on an excitation-level limitation. In addition, molecular orbitals are energy-optimized using multiconfigurational-self-consistent-field procedure for all these wave functions. The test cases include the symmetric dissociation of water (6-31G), N2 (6-31G), C2 (6-31G), and Be2 (cc-pVTZ). We find that the potential energy profile for H2O dissociation can be reasonably well described using only the Ω = 0 sector of the CI wave function. For the Be2 case, we show that the full CI potential energy curve (cc-pVTZ) is almost exactly reproduced using either Ω-based (including configurations having up to Ω = 2 in the virtual-orbital-space) or excitation-based (up to single-plus-double-substitutions) selection methods, both out of a full-valence-reference function. Finally, in dissociation cases of N2 and C2, we shall also consider novel hybrid wave functions obtained by a union of a set of CI configurations representing the full valence space and a set of CI configurations where seniority-number restriction is imposed for a complete set (full-valence-space and virtual) of correlated molecular orbitals, simultaneously. We discuss the usefulness of the seniority number concept in addressing both static and dynamic electron correlation problems along dissociation paths.
    Citation
    Bytautas, Laimutis, Scuseria, Gustavo E. and Ruedenberg, Klaus. "Seniority number description of potential energy surfaces: Symmetric dissociation of water, N2, C2, and Be2." The Journal of Chemical Physics, 143, no. 9 (2015) AIP Publishing LLC.: http://dx.doi.org/10.1063/1.4929904.
    Published Version
    http://dx.doi.org/10.1063/1.4929904
    Type
    Journal article
    Publisher
    AIP Publishing LLC.
    Citable link to this page
    https://hdl.handle.net/1911/94775
    Rights
    Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
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    • Chemistry Publications [705]
    • Faculty Publications [5504]

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    Managed by the Digital Scholarship Services at Fondren Library, Rice University
    Physical Address: 6100 Main Street, Houston, Texas 77005
    Mailing Address: MS-44, P.O.BOX 1892, Houston, Texas 77251-1892
    Site Map