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Direct minimization of the energy functional in LCAO-MO density matrix formalism

II. Multiconfiguration self-consistent-field theory for ground and excited states

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Abstract

The general multiconfiguration self-consistent-field method is presented along the density matrix formalism. The proposed optimization procedure for orbitals makes use of an orthogonal transformation in the space spanned by the fixed basis set. Acting on the unconstrained parameters of the transformation a direct minimization of the energy expression is performed using a gradient approach. A similar method may also be applied to the optimization of the expansion coefficients. The method works not only for the ground state of a given system, but also for any excited state, yielding an upper bound to the true energy of the considered state.

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Polezzo, S. Direct minimization of the energy functional in LCAO-MO density matrix formalism. Theoret. Chim. Acta 40, 245–252 (1975). https://doi.org/10.1007/BF00548459

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Key words

  • Direct energy minimization
  • Multiconfiguration self-consistent field