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Title: Electronic responses of long chains to electrostatic fields: Hartree-Fock vs. density-functional theory: A model study

The response to an electrostatic field is determined through simple model calculations, within both the restricted Hartree-Fock and density functional theory methods, for long, finite as well as infinite, periodic chains. The permanent dipole moment, μ{sub 0}, the polarizability, α, and the hyperpolarizabilities β and γ, calculated using a finite-field approach, are extensively analyzed. Our simple model allows for treatment of large systems and for separation of the properties into atomic and unit-cell contributions. That part of the response properties attributable to the terminations of the finite system change into delocalized current contributions in the corresponding infinite periodic system. Special emphasis is placed on analyzing the reasons behind the dramatic overestimation of the response properties found with density functional theory methods presently in common use.
Authors:
 [1] ;  [1] ;  [2] ;  [3]
  1. Physical and Theoretical Chemistry, University of Saarland, 66123 Saarbrücken (Germany)
  2. (China)
  3. Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106 (United States)
Publication Date:
OSTI Identifier:
22255142
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 5; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; DENSITY FUNCTIONAL METHOD; DIPOLE MOMENTS; HARTREE-FOCK METHOD; PERIODIC SYSTEM; POLARIZABILITY