Electron-correlation effects on the static longitudinal polarizability of polymeric chains

Champagne, Benoı̂t; Mosley, David H.; Vrac̆ko, Marjan; André, Jean‐Marie

doi:10.1103/physreva.52.178

Cited by 49 publications

(31 citation statements)

References 78 publications

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“…The KLI results for both a and g considerably improve upon LDA (for g the improvement is a factor of 6). However, the results are still not close to the HF and higher-level ab initio results [27]. In smaller chains, such as H 6 , we find g 31.3, 29.7 6 0.2, 36.7 6 0.2, and 99.7 6 0.2 3 10 3 a.u., for, respectively, MP4 [27], HF, KLI, and LDA, while for H 12 these numbers are 179, 147 6 2, 300 6 50, and 1250 6 50 3 10 3 a.u., showing that the LDA failure increases with chain length and that the problem is not restricted to conjugated molecules such as PA.…”

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confidence: 61%

“…However, the results are still not close to the HF and higher-level ab initio results [27]. In smaller chains, such as H 6 , we find g 31.3, 29.7 6 0.2, 36.7 6 0.2, and 99.7 6 0.2 3 10 3 a.u., for, respectively, MP4 [27], HF, KLI, and LDA, while for H 12 these numbers are 179, 147 6 2, 300 6 50, and 1250 6 50 3 10 3 a.u., showing that the LDA failure increases with chain length and that the problem is not restricted to conjugated molecules such as PA. In all cases, the KLI results partially correct the LDA͞GGA overpolarization (which we largely attribute to the linear term in this potential), but are still larger than the benchmark values.…”

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confidence: 61%

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Electric Field Dependence of the Exchange-Correlation Potential in Molecular Chains

et al. 1999

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Density functional calculations on the (non)linear optical properties of conjugated molecular chains using currently popular exchange-correlation (xc) potentials give overestimations of several orders of magnitude. By analyzing "exact" and Krieger-Li-Iafrate xc potentials, the error is traced back to an incorrect electric field dependence of the "response part" of the xc potential in local and gradientcorrected density approximations, which lack a linear term counteracting the applied electric field.PACS numbers: 31.15. Ew, 42.65.An, 71.15.Mb, 77.22.Ej The nonlinear optical (NLO) properties of molecules are of considerable current interest, both from the fundamental and technological points of view [1][2][3]. Prototype systems exhibiting large NLO responses like the polyacetylene (PA) chains have been studied intensively with conventional, ab initio Hartree-Fock (HF) based theoretical techniques [2]. Because density functional theory (DFT) [4,5] usually provides clearly improved accuracy with respect to HF at similar or lower computational cost, it seems tempting to apply DFT to the prediction of the NLO properties of large, conjugated molecular chains.Our calculations on static hyperpolarizabilities (determining the NLO response in the static limit) of such chains show, both here and in Ref. [6], that the local density approximation (LDA) and generalized gradient approximations (GGAs) in DFT provide very poor results. Whereas previously reported LDA errors are typically 10% for dielectric constants, we find overestimations of several orders of magnitude for the second hyperpolarizability g. In view of the respectable accuracy which is usually obtained in DFT calculations, this is highly surprising and deserves a detailed analysis, as this error may be among the largest in the history of DFT calculations. Our analysis allows us to pinpoint the weakness of the LDA. It will be shown below that, if an electric field, E, is applied, the so-called response part of the exact exchange-correlation (xc) potential develops a global behavior counteracting the applied field. Such behavior is not present in the LDA or GGA potentials. Our results substantiate and further elucidate the findings of Gonze, Ghosez, and Godby [7] and others [8][9][10][11][12][13], who pointed out the existence of such a counteracting linear potential in the exact y xc and provided the first physical interpretation for it [10,13].Description of the problem.-For this work, extensive calculations have been performed on PA and hydrogen chains. The LDA results described below have been obtained in the same manner as earlier calculations on the polarizability (a) and second hyperpolarizability (g) of C 60 [14]. Details of the computational procedure, the geometries, etc., have been given in another paper [6], where several aspects of the LDA problem (size of electron correlation correction, effect of bond length alternation) are described more fully.From the HF-based ab initio studies [15] on the NLO properties of PA chains, it is known that even sim...

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Electric Field Dependence of the Exchange-Correlation Potential in Molecular Chains

et al. 1999

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“…It is now well-known that Kohn-Sham time-dependent linear-response theory is not quantitatively accurate for heavily delocalized systems, with polarizabilities typically overestimated [29][30][31], and hyperpolarizabilities even more so. One may therefore question the validity of our calculations.…”

Section: Computational Details and Resultsmentioning

confidence: 99%

Anomalous nonadditive dispersion interactions in systems of three one-dimensional wires

Misquitta

Drummond

Stone³

et al. 2014

Phys. Rev. B

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The non-additive dispersion contribution to the binding energy of three one-dimensional (1D) wires is investigated using wires modelled by (i) chains of hydrogen atoms and (ii) homogeneous electron gases. We demonstrate that the non-additive dispersion contribution to the binding energy is significantly enhanced compared with that expected from Axilrod-Teller-Muto-type triple-dipole summations and follows a different power-law decay with separation. The triwire non-additive dispersion for 1D electron gases scales according to the power law d −β , where d is the wire separation, with exponents β(r s ) smaller than 3 and slightly increasing with r s from 2.4 at r s = 1 to 2.9 at r s = 10, where r s is the density parameter of the 1D electron gas. This is in good agreement with the exponent β = 3 suggested by the leading-order charge-flow contribution to the triwire nonadditivity, and is a significantly slower decay than the ∼ d −7 behaviour that would be expected from triple-dipole summations.

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“…1 and are compared with previous results [28,23,42]. For sake of a fair comparison, we have taken care of using the same pseudopotential as used in former calculations because we found that using different pseudopotentials leads to different absolute values of the highly sensitive polarizabilities.…”

Section: Hydrogen Chainsmentioning

confidence: 97%

Polarizabilities as a test of localized approximations to the self-interaction correction

Messud

Wang

Dinh

et al. 2009

Chemical Physics Letters

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We present applications of the recently introduced "Generalized SIC-Slater" scheme which provides a simple Self-Interaction Correction approximation in the framework of the Optimized Effective Potential. We focus on the computation of static polarizabilities which are known to constitute stringent tests for Density Functional Theory. We apply the new method to model H chains, but also to more realistic systems such as C 4 (organic) chains, and less symmetrical systems such as a Na 5 (metallic) cluster. Comparison is made with other SIC schemes, especially with the standard SIC-Slater one.

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Electron-correlation effects on the static longitudinal polarizability of polymeric chains

Cited by 49 publications

References 78 publications

Electric Field Dependence of the Exchange-Correlation Potential in Molecular Chains

Electric Field Dependence of the Exchange-Correlation Potential in Molecular Chains

Anomalous nonadditive dispersion interactions in systems of three one-dimensional wires

Polarizabilities as a test of localized approximations to the self-interaction correction

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