Abstract
Basing on minimization methods, earlier suggested algorithms for the solution of a many-electron problem in Hartree-Fock-Roothaan approximation for systems with close and open shells extend over Roothaan-Hartree-Fock atomic theory (Roothaan-Bagus method). In present work the expressions for energy derivatives with respect to elements of density matrices and nonlinear parameters of atomic orbitals — orbital exponents — have been obtained to solve Hartree-Fock (HF) equations in algebraic approximation. It is possible to create an algorithm of the first-order minimization or quasi-Newton method on their basis. Calculations of atoms and ions with several open shells were carried out by minimization methods. The energy values, close to the results of numerical solution of HF equations with high accuracy of virial relation, were gained using a sufficiently narrow basic set of Slater-type AO.
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Original Russian Text Copyright © 2005 by Yu. B. Malykhanov and S. A. Romanov
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Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No.2, pp. 212–220, March–April, 2005.
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Malykhanov, Y.B., Romanov, S.A. Application of minimization methods in calculating atoms with several open shells. J Struct Chem 46, 204–212 (2005). https://doi.org/10.1007/s10947-006-0032-2
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DOI: https://doi.org/10.1007/s10947-006-0032-2