Real-space calculations of atomic and molecular polarizabilities using asymptotically correct exchange-correlation potentials

Journal Article · Thu Jul 15 04:00:00 EDT 2010 · Physical Review. A

DOI:https://doi.org/10.1103/PHYSREVA.82.012502· OSTI ID:21442906

Vasiliev, Igor; Chelikowsky, James R ^[1]

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1. Department of Physics, New Mexico State University, Las Cruces, New Mexico 88003 (United States)

The static electric dipole polarizabilities for a variety of atoms and molecules are calculated using a finite-field method based on ab initio pseudopotential density functional theory. The calculations are performed in real space without an explicit basis. We employ different representations of the exchange-correlation potential: the local density approximation, generalized gradient approximation, and asymptotically corrected functionals introduced by van Leeuwen and Baerends and by Casida and Salahub. Our calculations show that the computed values of polarizabilities are strongly influenced by the asymptotic behavior of the density functional exchange-correlation potential. The accuracy of theoretical atomic and molecular polarizabilities is substantially improved by the use of asymptotically correct exchange-correlation functionals. This result can be explained in terms of electronic excitation energies and the polarizability sum rule.

• OSTI ID: 21442906
• Journal Information: Physical Review. A, Journal Name: Physical Review. A Journal Issue: 1 Vol. 82; ISSN 1050-2947; ISSN PLRAAN
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
ACCURACY
APPROXIMATIONS
ASYMPTOTIC SOLUTIONS
ATOMS
CALCULATION METHODS
CORRELATIONS
DENSITY
DENSITY FUNCTIONAL METHOD
DIPOLES
ELECTRIC DIPOLES
ELECTRICAL PROPERTIES
ENERGY-LEVEL TRANSITIONS
EQUATIONS
EXCITATION
FUNCTIONALS
FUNCTIONS
MATHEMATICAL SOLUTIONS
MOLECULES
MULTIPOLES
PHYSICAL PROPERTIES
POLARIZABILITY
POTENTIALS
SPACE
SUM RULES
VARIATIONAL METHODS