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Structure of the correlation–kinetic component of the Kohn–Sham exchange potential in atoms and at metal surfaces
Author(s) -
Solomatin Alexander,
Sahni Viraht
Publication year - 1997
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/(sici)1097-461x(1997)65:5<893::aid-qua53>3.0.co;2-x
Subject(s) - kohn–sham equations , kinetic energy , pauli exclusion principle , chemistry , atomic orbital , density matrix , virial theorem , density functional theory , atomic physics , kinetic term , physics , field (mathematics) , quantum mechanics , electron , computational chemistry , quantum , mathematics , scalar field , galaxy , pure mathematics
The Kohn–Sham density functional theory “exchange” potential v x ( r )=δ E x KS [ρ]/δρ( r ), where E x KS [ρ] is the “exchange” energy functional, is composed of a component representative of Pauli correlations and one that constitutes part of the correlation contribution to the kinetic energy. The Pauli term is the work done W x KS ( r ) in the field ℰ x KS ( r ) obtained by Coulomb's law from the Fermi hole charge distribution constructed from the Kohn–Sham orbitals. The correlation–kinetic term is the work done W t c(1) ( r ) in the field Z t c(1) ( r ) derived from the kinetic‐energy–density tensor involving the first‐order correction to the Kohn–Sham single‐particle density matrix. The sum of these fields is conservative, so that the total work done is path‐independent. There is no explicit correlation–kinetic contribution to the “exchange” energy E x KS [ρ]. Its contribution is manifested via the Kohn–Sham orbitals generated via the potential v x ( r ). The functional E x KS [ρ] is thus expressed in virial form entirely in terms of the Pauli field ℰ x KS ( r ). In this article, we determine and study the structure of the correlation–kinetic component field Z t c(1) ( r ) and work W t c(1) ( r ) for the nonuniform electron density system in atoms and at metal surfaces. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 65 : 893–906, 1997