A comparison of density-functional-theory and coupled-cluster frequency-dependent polarizabilities and hyperpolarizabilities

The frequency-dependent polarizabilities and hyperpolarizabilities of HF, CO, H 2 O and para-nitroaniline calculated by density-functional theory are compared with accurate coupled-cluster results. Whereas the local-density approximation and the generalized gradient approximation (BLYP) perform very...

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Bibliographic Details
Published inMolecular physics Vol. 103; no. 2-3; pp. 439 - 450
Main Authors Sałek ¶, Paweł, Helgaker, Trygve, Vahtras, Olav, Ågren, Hans, Jonsson ⊥, Dan, Gauss, Jürgen
Format Journal Article
LanguageEnglish
Published Taylor & Francis Group 20.01.2005
Subjects
2nd-order
approximation
dispersion
doubles model
energies
exchange
hartree-fock
local-density
para-nitroaniline
small molecules
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Summary:The frequency-dependent polarizabilities and hyperpolarizabilities of HF, CO, H 2 O and para-nitroaniline calculated by density-functional theory are compared with accurate coupled-cluster results. Whereas the local-density approximation and the generalized gradient approximation (BLYP) perform very similarly and overestimate polarizabilities and, in particular, the hyperpolarizabilities, hybrid density-functional theory (B3LYP) performs better and produces results similar to those obtained by coupled-cluster singles-and-doubles theory. Comparisons are also made for singlet excitation energies, calculated using linear response theory.
ISSN:0026-8976
1362-3028
1362-3028
DOI:10.1080/00268970412331319254