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PROJECTION OF SINGLE-DETERMINANT SOLUTIONS OF SPIN-POLARIZED SELF-CONSISTENT FIELD EQUATIONS IN THE BASIS SET OF SPIN-PAIRED ORBITALS

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Abstract

A new scheme is presented for obtaining a pure spin state for the one-determinant wave function built on Hartree–Fock or Kohn–Sham orbitals. In this scheme, the unrestricted determinant is expanded in restricted determinants constructed in the basis set of spin-paired orbitals. Using spin projection, one can determine spin density components corresponding to pure spin states and estimate the weight of spin contaminants in the spin density. The efficiency of this approach is demonstrated on the example of methane oxidation. It is shown that self-consistent solutions of Hartree–Fock or Kohn–Sham equations with broken spin symmetry are not an artifact of one-determinant approximation. The equations reflect real spin polarization that creates negative spin density in some parts of the molecular system.

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  1. * The program was created by S. F. Ruzankin and D. A. Ovchinnikov and can be freely requested from the authors at s_ruz@bk.ru

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Authors and Affiliations

  1. Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia

    D. A. Ovchinnikov, S. F. Ruzankin, V. Yu. Kovalskii & I. L. Zilberberg

  2. Novosibirsk State University, Novosibirsk, Russia

    D. A. Ovchinnikov & I. L. Zilberberg

  3. Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia

    V. Yu. Kovalskii & I. L. Zilberberg

Authors
  1. D. A. Ovchinnikov
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  2. S. F. Ruzankin
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  3. V. Yu. Kovalskii
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  4. I. L. Zilberberg
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Correspondence to I. L. Zilberberg.

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Russian Text © The Author(s), 2021, published in Zhurnal Strukturnoi Khimii, 2021, Vol. 62, No. 8, pp. 1231-1250.https://doi.org/10.26902/JSC_id76103

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Ovchinnikov, D.A., Ruzankin, S.F., Kovalskii, V.Y. et al. PROJECTION OF SINGLE-DETERMINANT SOLUTIONS OF SPIN-POLARIZED SELF-CONSISTENT FIELD EQUATIONS IN THE BASIS SET OF SPIN-PAIRED ORBITALS. J Struct Chem 62, 1147–1166 (2021). https://doi.org/10.1134/S0022476621080011

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