Assessment of conventional density functional schemes for computing the polarizabilities and hyperpolarizabilities of conjugated oligomers
| Autor: | Evert Jan Baerends, J. G. Snijders, Benoît Champagne, Bernard Kirtman, E A Perpète, S. J. A. van Gisbergen, Kathleen A. Robins, C. Soubra-Ghaoui |
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| Přispěvatelé: | Theoretical Chemistry |
| Jazyk: | angličtina |
| Rok vydání: | 1998 |
| Předmět: |
VIBRATIONAL FREQUENCIES
STATIC LONGITUDINAL POLARIZABILITY Ab initio NONLINEAR-OPTICAL-PROPERTIES General Physics and Astronomy Hyperpolarizability Molecular physics Polyacetylene chemistry.chemical_compound Ab initio quantum chemistry methods Polarizability Electric field Physical and Theoretical Chemistry COUPLED HARTREE-FOCK ELECTRON-CORRELATION Condensed matter physics Electronic correlation Chemistry CLOSED-SHELL ATOMS EXCHANGE-CORRELATION POTENTIALS CORRECT ASYMPTOTIC-BEHAVIOR SDG 1 - No Poverty SELF-INTERACTION CORRECTION Density functional theory FREQUENCY-DEPENDENT POLARIZABILITIES |
| Zdroj: | Champagne, B, Perpète, E A, van Gisbergen, S J A, Baerends, E J, Snijders, J G, Soubra-Ghaoui, C, Robins, K A & Kirtman, B 1998, ' Assessment of Conventional Density Functional Schemes for Computing the Polarizabilities and hyperpolarizabilities of Conjugated Oligomers: An Ab Initio Investigation of Polyacetylene Chains ', Journal of Chemical Physics, vol. 109, pp. 10489-10498 . https://doi.org/10.1063/1.477731 Journal of Chemical Physics, 109(23), 10489-10498. AMER INST PHYSICS Journal of Chemical Physics, 109, 10489-10498. American Institute of Physics Publising LLC |
| ISSN: | 0021-9606 |
| DOI: | 10.1063/1.477731 |
| Popis: | DFT schemes based on conventional and less conventional exchange-correlation (XC) functionals have been employed to determine the polarizability and second hyperpolarizability of π-conjugated polyacetylene chains. These functionals fail in one or more of several ways: (i) the correlation correction to α is either much too small or in the wrong direction, leading to an overestimate; (ii) γ is significantly overestimated; (iii) the chain length dependence is excessively large, particularly for γ and for the more alternant system; and (iv) the bond length alternation effects on γ are either underestimated or qualitatively incorrect. The poor results with the asymptotically correct van Leeuwen-Baerends XC potential show that the overestimations are not related to the asymptotic behavior of the potential. These failures are described in terms of the separate effects of the exchange and the correlation parts of the XC functionals. They are related to the short-sightedness of the XC potentials which are relatively insensitive to the polarization charge induced by the external electric field at the chain ends. © 1998 American Institute of Physics. |
| Databáze: | OpenAIRE |
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