TY - JOUR
T1 - Calculation of electric dipole (hyper)polarizabilities by long-range-correction scheme in density functional theory
T2 - A systematic assessment for polydiacetylene and polybutatriene oligomers
AU - Kirtman, Bernard
AU - Bonness, Sean
AU - Ramirez-Solis, Alejandro
AU - Champagne, Benoit
AU - Matsumoto, Hironori
AU - Sekino, Hideo
PY - 2008/3/28
Y1 - 2008/3/28
N2 - The long-range correction (LC) for treating electron exchange in density functional theory, combined with the Becke-Lee-Yang-Parr (BLYP) exchange-correlation functional, was used to determine (hyper)polarizabilities of polydiacetylene/polybutatriene oligomers. In comparison with coupled-cluster calculations including single and double excitations as well as a perturbative treatment of triple excitations, our values indicate that the tendency of conventional functionals to result in a catastrophic overshoot for these properties is alleviated but not eliminated. No clear-cut preference for LC-BLYP over Hartree-Fock values is obtained. This analysis is consistent with the calculations of Sekino [J. Chem. Phys. 126, 014107 (2007)] on polyacetylene and molecular hydrogen oligomers. Thus, the performance of LC-BLYP with regard to (hyper)polarizabilities of quasilinear conjugated systems is now well characterized.
AB - The long-range correction (LC) for treating electron exchange in density functional theory, combined with the Becke-Lee-Yang-Parr (BLYP) exchange-correlation functional, was used to determine (hyper)polarizabilities of polydiacetylene/polybutatriene oligomers. In comparison with coupled-cluster calculations including single and double excitations as well as a perturbative treatment of triple excitations, our values indicate that the tendency of conventional functionals to result in a catastrophic overshoot for these properties is alleviated but not eliminated. No clear-cut preference for LC-BLYP over Hartree-Fock values is obtained. This analysis is consistent with the calculations of Sekino [J. Chem. Phys. 126, 014107 (2007)] on polyacetylene and molecular hydrogen oligomers. Thus, the performance of LC-BLYP with regard to (hyper)polarizabilities of quasilinear conjugated systems is now well characterized.
UR - http://www.scopus.com/inward/record.url?scp=41049095335&partnerID=8YFLogxK
U2 - 10.1063/1.2885051
DO - 10.1063/1.2885051
M3 - Article
AN - SCOPUS:41049095335
SN - 0021-9606
VL - 128
JO - The journal of chemical physics
JF - The journal of chemical physics
IS - 11
M1 - 114108
ER -