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Multi-reference Hartree-Fock configuration interaction calculations of LiH and Be using a new double-zeta atomic base

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Abstract

In this work, we propose new double-zeta atomic bases for the Li and Be atoms. These were obtained by applying the Hartree-Fock-Gauss generalized simulated annealing (GSA) method—a modified form of the GSA algorithm. The new bases were generated through optimization of the atomic electronic energy functional with regards to the linear combination of atomic orbitals-molecular orbital (LCAO-MO) coefficients, and exponent and contraction coefficients of the primitive Gaussian functions, simultaneously. These new bases were tested by performing calculations of the ground state energy of the Be atom, and the ground state energy and permanent electrical dipole moment of the LiH molecule, using the multi-reference Hartree-Fock (HF) configuration interaction method—a multi-reference method based on multiple HF solutions. In addition, multi-reference HF configuration interaction calculations were performed for the Be atom using the standard double-zeta, triple-zeta and polarized double-zeta bases. With the new double-zeta bases and with reduced multi-reference HF bases, it was possible to obtain lower energies than those obtained with the full configuration interaction calculations using the standard double-zeta bases and dipole moment values in close agreement with experimental values.

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Notes

  1. In this work all calculations for the LiH molecule were performed using the new dz atomic base for the Li atom and the standard dz atomic base for the H atom.

  2. The sets of LCAO-MO coefficients for the HF solutions can be obtained on request.

  3. The MRHF bases employed in the MRHFCI calculations can be obtained on request.

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Acknowledgments

The authors acknowledge Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) and Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro (FAPERJ) for financial support.

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Authors and Affiliations

  1. Departamento de Física do Estado Sólido, Instituto de Física da UFBA, Salvador, Brazil

    Antonio Moreira de Cerqueira Sobrinho, Micael Dias de Andrade & Luiz Augusto Carvalho Malbouisson

  2. Departamento de Físico-Química, Instituto de Química da UFRJ, Rio de Janeiro, Brazil

    Antonio Moreira de Cerqueira Sobrinho, Marco Antônio Chaer Nascimento & Luiz Augusto Carvalho Malbouisson

Authors
  1. Antonio Moreira de Cerqueira Sobrinho
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  2. Micael Dias de Andrade
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  3. Marco Antônio Chaer Nascimento
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  4. Luiz Augusto Carvalho Malbouisson
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Corresponding author

Correspondence to Luiz Augusto Carvalho Malbouisson.

Additional information

This paper belongs to Topical Collection Brazilian Symposium of Theoretical Chemistry (SBQT2013)

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de Cerqueira Sobrinho, A.M., de Andrade, M.D., Nascimento, M.A.C. et al. Multi-reference Hartree-Fock configuration interaction calculations of LiH and Be using a new double-zeta atomic base. J Mol Model 20, 2382 (2014). https://doi.org/10.1007/s00894-014-2382-6

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  • DOI: https://doi.org/10.1007/s00894-014-2382-6

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