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Quantal density functional theory of the hydrogen molecule.

Authors :
Xiao-Yin Pan
Sahni, Viraht
Source :
Journal of Chemical Physics; 3/22/2004, Vol. 120 Issue 12, p5642-5649, 8p, 13 Graphs
Publication Year :
2004

Abstract

In this paper we perform a quantal density functional theory (Q-DFT) study of the hydrogen molecule in its ground state. In common with traditional Kohn–Sham density functional theory, Q-DFT transforms the interacting system as described by Schrödinger theory, to one of noninteracting fermions—the S system—such that the equivalent density, total energy, and ionization potential are obtained. The Q-DFT description of the S system is in terms of “classical” fields and their quantal sources that are quantum-mechanical expectations of Hermitian operators taken with respect to the interacting and S system wave functions. The sources, and hence the fields, are separately representative of all the many-body effects the S system must account for, viz. electron correlations due to the Pauli exclusion principle, Coulomb repulsion, and correlation-kinetic effects. The local electron-interaction potential energy of each model fermion is the work done to move it in the force of a conservative effective field that is the sum of the individual fields. The Hartree, Pauli, Coulomb, and correlation-kinetic energy components of the total energy are also expressed in virial form in terms of the corresponding fields. The highest occupied eigenvalue of the S system is the negative of the ionization potential energy. The Q-DFT analysis of the hydrogen molecule is performed employing the highly accurate correlated wave function of Kolos and Roothaan. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Details

Language :
English
ISSN :
00219606
Volume :
120
Issue :
12
Database :
Complementary Index
Journal :
Journal of Chemical Physics
Publication Type :
Academic Journal
Accession number :
12512627
Full Text :
https://doi.org/10.1063/1.1647514