Calculation of electric dipole (hyper)polarizabilities by long-range-correction scheme in density functional theory: a systematic assessment for polydiacetylene and polybutatriene oligomers |
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Authors: | Kirtman Bernard Bonness Sean Ramirez-Solis Alejandro Champagne Benoit Matsumoto Hironori Sekino Hideo |
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Institution: | Department of Chemistry & Biochemistry, University of California, Santa Barbara, CA 93106-9510, USA. |
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Abstract: | 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 et al. 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. |
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