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Issue 34, 2016
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Separation of dynamic and nondynamic correlation

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Abstract

The account of electron correlation and its efficient separation into dynamic and nondynamic parts plays a key role in the development of computational methods. In this paper we suggest a physically-sound matrix formulation to split electron correlation into dynamic and nondynamic parts using the two-particle cumulant matrix and a measure of the deviation from idempotency of the first-order density matrix. These matrices are applied to a two-electron model, giving rise to a simplified electron correlation index that (i) depends only on natural orbitals and their occupancies, (ii) can be straightforwardly decomposed into orbital contributions and (iii) splits into dynamic and nondynamic correlation parts that (iv) admit a local version. These expressions are shown to account for dynamic and nondynamic correlation in a variety of systems containing different electron correlation regimes, thus providing the first separation of dynamic and nondynamic correlation using solely natural orbital occupancies.

Graphical abstract: Separation of dynamic and nondynamic correlation

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Publication details

The article was received on 06 May 2016, accepted on 18 Jul 2016 and first published on 29 Jul 2016


Article type: Paper
DOI: 10.1039/C6CP03072F
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Citation: Phys. Chem. Chem. Phys., 2016,18, 24015-24023
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    Separation of dynamic and nondynamic correlation

    E. Ramos-Cordoba, P. Salvador and E. Matito, Phys. Chem. Chem. Phys., 2016, 18, 24015
    DOI: 10.1039/C6CP03072F

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