Polarizability and second hyperpolarizability evaluation of long molecules by the density functional theory with long-range correction.
Polarizabilities and second hyperpolarizabilities of polyacetylene and a hydrogen chain are evaluated by density functional theory (DFT) using a hybrid generalized gradient approximation functional with correct long-range electron-electron interactions. The well known catastrophic overestimate of the hyperpolarizabilities for molecular systems of enhanced length is corrected by the two-electron repulsion operator decomposition technique, integrating the distance-dependent nonlocal exchange effects for long-range interaction, while neither the asymptotically corrected exchange functional for long-range interaction nor ordinary hybrid methods seem to be capable of overcoming the serious drawback of the DFT in polarizability/hyperpolarizability evaluation.
Sekino
Hideo
H
Toyohashi University of Technology (JST-CREST), Hibarigaoka, Tenpaku-cho, Toyohashi, Aichi 441-8580, Japan. sekino@tutkie.tut.ac.jp
Maeda
Yasuyuki
Y
Kamiya
Muneaki
M
Hirao
Kimihiko
K