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Depurated inversion method for orbital‐specific exchange potentials
Author(s) -
Mendez Alejandra M. P.,
Mitnik Darío M.,
Miraglia Jorge E.
Publication year - 2016
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25295
Subject(s) - wave function , atomic orbital , inversion (geology) , chemistry , eigenvalues and eigenvectors , configuration interaction , ground state , hartree–fock method , molecular orbital , atomic physics , computational chemistry , boundary value problem , quantum mechanics , physics , excited state , molecule , electron , paleontology , structural basin , biology
This work presents exchange potentials for specific orbitals calculated by inverting Hartree–Fock wavefunctions. This was achieved by using a Depurated Inversion Method. The basic idea of the method relies on the substitution of Hartree–Fock orbitals and eigenvalues into the Kohn–Sham equation. Through inversion, the corresponding effective potentials were obtained. Further treatment of the inverted potential should be carried on. The depuration is a careful optimization which eliminates the poles and also ensures the fullfilment of the appropriate boundary conditions. The procedure developed here is not restricted to the ground state or to a nodeless orbital and is applicable to all kinds of atoms. As an example, exchange potentials for noble gases and term‐dependent orbitals of the lower configuration of Nitrogen are calculated. The method allows to reproduce the input energies and wavefunctions with a remarkable degree of accuracy.