Stretched hydrogen molecule from a constrained-search density-functional perspective

Constrained-search density functional theory gives valuable insights into the fundamentals of density functional theory. It provides exact results and bounds on the ground- and excited-state density functionals. An important advantage of the theory is that it gives guidance in the construction of fu...

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Bibliographic Details
Published in:Physical review. A, Atomic, molecular, and optical physics Atomic, molecular, and optical physics, 2009-10, Vol.80 (4), Article 042501
Main Authors: Valone, Steven M., Levy, Mel
Format: Article
Language:English
Subjects:
CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS
CONSTRUCTION
ELECTRON CORRELATION
ENERGY GAP
FUNCTIONALS
HAMILTONIANS
HYDROGEN
VALENCE
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Summary:Constrained-search density functional theory gives valuable insights into the fundamentals of density functional theory. It provides exact results and bounds on the ground- and excited-state density functionals. An important advantage of the theory is that it gives guidance in the construction of functionals. Here they engage constrained search theory to explore issues associated with the functional behavior of 'stretched bonds' in molecular hydrogen. A constrained search is performed with familiar valence bond wavefunctions ordinarily used to describe molecular hydrogen. The effective, one-electron hamiltonian is computed and compared to the corresponding uncorrelated, Hartree-Fock effective hamiltonian. Analysis of the functional suggests the need to construct different functionals for the same density and to allow a competition among these functions. As a result the correlation energy functional is composed explicitly of energy gaps from the different functionals.
ISSN:1050-2947
1094-1622
DOI:10.1103/PhysRevA.80.042501