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
Y1 - 1999/12/1
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.
KW - Bond length alternation
KW - Electron correlation
KW - Polarizability and second hyperpolarizability
KW - Polyacetylene chains
UR - http://www.scopus.com/inward/record.url?scp=0009347355&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0009347355
SN - 0020-7608
VL - 75
SP - 441
EP - 447
JO - International Journal of Quantum Chemistry
JF - International Journal of Quantum Chemistry
IS - 4-5
ER -