Influence of the long-range exchange effect on dynamic polarizability
| Autor: | Yasuyuki Maeda, Hideo Sekino, Muneaki Kamiya |
|---|---|
| Rok vydání: | 2005 |
| Předmět: |
Density matrix
Chemistry Biophysics Cauchy distribution Equations of motion Time-dependent density functional theory Condensed Matter Physics Molecular physics Adiabatic theorem Polarizability Quantum mechanics Physics::Atomic and Molecular Clusters Partition (number theory) Density functional theory Physics::Chemical Physics Physical and Theoretical Chemistry Molecular Biology |
| Zdroj: | Molecular Physics. 103:2183-2189 |
| ISSN: | 1362-3028 0026-8976 |
| DOI: | 10.1080/00268970500083994 |
| Popis: | The long-range interaction in density functional theory (DFT) is corrected using a partition technique of the two-electron operator when applied in the equation of motion (EOM) on the first-order density matrix. While the correction produces a minor effect on the static polarizabilities of small molecules, it improves the overestimated Cauchy coefficients of small molecules by the DFT without the correction. The same technique is applied to compute the polarizabilities of long chain molecules, a long standing problem of DFT. The overestimations by the DFT without the correction are remarkably improved for hydrogen chains and polyacetylene. Finally, the method is applied to compute the dynamic polarizabilities of C4H6 and C12H14. The frequency dependencies obtained by the DFT with the long-range correction (LRC) are different from that obtained by the DFT without LRC and similar to that obtained by the HF. The adiabatic approximation taken in the TDDFT of the first-order density matrix without LRC causes c... |
| Databáze: | OpenAIRE |
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