Bond length alternation effects on the static electronic polarizability and second hyperpolarizability of polyacetylene chains

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Abstract

The static electronic longitudinal polarizability (α) and second hyperpolarizability (γ) of all-trans planar polyacetylene chains have been computed at different levels of approximation by varying the bond length alternation (BLA) along the conjugated backbone. Although the restricted Hartree-Fock (RHF) and second-order Møller-Plesset (MP2) approaches exhibit the expected behavior, i.e., the smaller the BLA, the larger the γ, the density functional schemes based on the SVWN and B3LYP exchange correlation functionals behave in a totally different way. when BLA increases, γ first increases, attains a maximum, and then decreases. Moreover, the RHF approach is found to overestimate by a factor of 2-3 the BLA dependence of α with respect to the MP2 procedure.

Original languageEnglish
Pages (from-to)441-447
Number of pages7
JournalInternational Journal of Quantum Chemistry
Volume75
Issue number4-5
Publication statusPublished - 1 Dec 1999

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Polyacetylenes
polyacetylene
alternations
Bond length
electronics
functionals
approximation

Keywords

  • Bond length alternation
  • Electron correlation
  • Polarizability and second hyperpolarizability
  • Polyacetylene chains

Cite this

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title = "Bond length alternation effects on the static electronic polarizability and second hyperpolarizability of polyacetylene chains",
abstract = "The static electronic longitudinal polarizability (α) and second hyperpolarizability (γ) of all-trans planar polyacetylene chains have been computed at different levels of approximation by varying the bond length alternation (BLA) along the conjugated backbone. Although the restricted Hartree-Fock (RHF) and second-order M{\o}ller-Plesset (MP2) approaches exhibit the expected behavior, i.e., the smaller the BLA, the larger the γ, the density functional schemes based on the SVWN and B3LYP exchange correlation functionals behave in a totally different way. when BLA increases, γ first increases, attains a maximum, and then decreases. Moreover, the RHF approach is found to overestimate by a factor of 2-3 the BLA dependence of α with respect to the MP2 procedure.",
keywords = "Bond length alternation, Electron correlation, Polarizability and second hyperpolarizability, Polyacetylene chains",
author = "Beno{\^i}t Champagne and Perp{\`e}te, {Eric A.}",
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TY - JOUR

T1 - Bond length alternation effects on the static electronic polarizability and second hyperpolarizability of polyacetylene chains

AU - Champagne, Benoît

AU - Perpète, Eric A.

PY - 1999/12/1

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N2 - The static electronic longitudinal polarizability (α) and second hyperpolarizability (γ) of all-trans planar polyacetylene chains have been computed at different levels of approximation by varying the bond length alternation (BLA) along the conjugated backbone. Although the restricted Hartree-Fock (RHF) and second-order Møller-Plesset (MP2) approaches exhibit the expected behavior, i.e., the smaller the BLA, the larger the γ, the density functional schemes based on the SVWN and B3LYP exchange correlation functionals behave in a totally different way. when BLA increases, γ first increases, attains a maximum, and then decreases. Moreover, the RHF approach is found to overestimate by a factor of 2-3 the BLA dependence of α with respect to the MP2 procedure.

AB - The static electronic longitudinal polarizability (α) and second hyperpolarizability (γ) of all-trans planar polyacetylene chains have been computed at different levels of approximation by varying the bond length alternation (BLA) along the conjugated backbone. Although the restricted Hartree-Fock (RHF) and second-order Møller-Plesset (MP2) approaches exhibit the expected behavior, i.e., the smaller the BLA, the larger the γ, the density functional schemes based on the SVWN and B3LYP exchange correlation functionals behave in a totally different way. when BLA increases, γ first increases, attains a maximum, and then decreases. Moreover, the RHF approach is found to overestimate by a factor of 2-3 the BLA dependence of α with respect to the MP2 procedure.

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KW - Electron correlation

KW - Polarizability and second hyperpolarizability

KW - Polyacetylene chains

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