Ultranonlocality in Time-Dependent Current-Density-Functional Theory: Application to Conjugated Polymers

Faassen, Meta van; Boeij, P.L. de; Leeuwen, Robert van; Berger, J. A.; Snijders, J.G.

doi:10.1103/physrevlett.88.186401

Cited by 230 publications

(246 citation statements)

References 25 publications

(30 reference statements)

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“…As shown in ref 48, accurately predicting the polarizability of the H 2 linear chain is particularly difficult for semilocal functionals. Figure 2 presents the longitudinal polarizability per H 2 fragment for oligomers of various lengths and the periodic chain.…”

Section: Polarizabilities In H 2 Chainsmentioning

confidence: 99%

Assessment of a Middle-Range Hybrid Functional

Henderson

Izmaylov

Scuseria

et al. 2008

J. Chem. Theory Comput.

163

140

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While hybrid functionals are largely responsible for the utility of modern Kohn-Sham density functional theory, they are not without their weaknesses. In the solid state, the slow decay of their nonlocal Hartree-Fock-type exchange makes hybrids computationally demanding and can introduce unphysical effects. Both problems can be remedied by a screened hybrid which uses exact exchange only at short-range. Many molecular properties, in contrast, benefit from the inclusion of long-range exact exchange. Recently, the authors reconciled these two seemingly contradictory requirements by introducing the HISS functional [J. Chem. Phys. 2007, 127, 221103], which uses exact exchange only in the middle range. In this paper, we expand upon our previous work, benchmarking the performance of the HISS functional for several simple properties and applying it to the dissociation of homonuclear diatomic cations and to the polarizability of linear H 2 chains to determine the importance of middle-range exact exchange for these systems, which are expected to be sensitive to the asymptotic exchange potential.

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Section: Polarizabilities In H 2 Chainsmentioning

confidence: 99%

Assessment of a Middle-Range Hybrid Functional

Henderson

Izmaylov

Scuseria

et al. 2008

J. Chem. Theory Comput.

163

140

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“…It is found that the values of ␣ av DFPT for the two polymers are in reasonable agreement with typical data for the axial polarizability of conjugated polymers. 16,17 The calculated permittivity values of PPyV also show strong anisotropy, with ␤ zz ӷ ␤ yy and ␤ xx Ӎ ␤ yy . The average PPyV permittivity ␤ av is 2.10 ͑compared to 2.15 for PPV͒.…”

Section: B Electric Field Responsementioning

confidence: 99%

“…However, despite these results, no comprehensive study is available concerning the dynamical properties of the materials, especially the dynamical anisotropy. Realistic firstprinciples calculations are a way forward but they are computationally very demanding and it is often the case that the calculations of the dynamical properties are of the average axial values for simple polymers only, 16,17 while ignoring the anisotropy information. Nevertheless, some progress has been made in understanding the anisotropy of the polarizability for molecules and molecular crystals [18][19][20][21] and for the dielectric and vibrational properties of some of the simpler amino acid molecules.…”

Section: Introductionmentioning

confidence: 99%

Lattice dynamics of polyaniline and poly(p-pyridyl vinyline): First-principles determination

et al. 2006

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The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. First-principles density functional studies of the dynamical properties of the conjugated polymers polyaniline and poly͑p-pyridyl vinyline͒ are presented in this work. We have employed linear response within density functional perturbation theory, as implemented in the CASTEP code, to investigate the Born effective charges, polarizabilities, and vibrational properties. With regard to the last, we have calculated the vibrational frequencies and made assignments of the modes for the two polymers. Most of the phonon modes have been classified and we have shown that the higher frequency modes are associated with C u H and C v N stretching modes. We also present the results of calculations of the polarizability and permittivity of the materials which are in reasonable agreement with the typical values of conjugated polymers. Dynamical Born effective charges have been calculated and compared with the Mulliken population atomic charges. It is found that notable differences exist between the Born effective charges for the nitrogen atoms in the conducting polymers, and we conclude that effective charges are more appropriate for use in the study of the dynamics of the systems. Differences are found in the ir absorption spectra obtained for the two polymers, which can be attributed to the structural differences of the two materials. It is found that the presence of the nitrogen atom plays an important role in determining their lattice dynamics.

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“…28 However, to obtain results in good agreement with experiment, an empirical prefactor had to be used. Later van Faassen et al 19,20 showed that the inclusion of the VK functional in TDDFT calculations yields greatly improved polarizabilities for -conjugated polymers, obtaining results that are comparable to MP2 values. These results were indications that the VK formalism is a very promising one, even when it is applied to describe phenomena related to the particle-hole regime in systems of which the ground-state density nor the induced current density is slowly varying.…”

mentioning

confidence: 99%

“…16 Third, to describe nonlocal exchange-correlation effects in large systems, 15,17,18 it can be more convenient and more efficient to use a local functional of the current density instead of a nonlocal functional of the density. [19][20][21] Within TDDFT, one would need an exchange-correlation functional that is completely nonlocal to be able to take into account the charges that are induced at the surface of the system caused by the external field and that produce a counteracting field. 13,22 Instead, by applying a local functional of the current density, we can still take into account nonlocal effects that are induced in the system by an external field.…”

Section: Introductionmentioning

confidence: 99%

Analysis of the Vignale-Kohn current functional in the calculation of the optical spectra of semiconductors

2007

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Analysis of the Vignale-Kohn current functional in the calculation of the optical spectra of semiconductors Berger, J. A.; de Boeij, P. L.; van Leeuwen, R. Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. In this work, we investigate the Vignale-Kohn current functional when applied to the calculation of optical spectra of semiconductors. We discuss our results for silicon. We found qualitatively similar results for other semiconductors. These results show that there are serious limitations to the general applicability of the VignaleKohn functional. We show that the constraints on the degree of nonuniformity of the ground-state density and on the degree of the spatial variation of the external potential under which the Vignale-Kohn functional was derived are almost all violated. We argue that the Vignale-Kohn functional is not suited to use in the calculation of optical spectra of semiconductors since the functional was derived for a weakly inhomogeneous electron gas in the region above the particle-hole continuum, whereas the systems we study are strongly inhomogeneous and the absorption spectrum is closely related to the particle-hole continuum. DOI: 10.1103/PhysRevB.75.035116 PACS number͑s͒: 71.45.Gm, 31.15.Ew, 78.20.Ϫe, 78.66.Db I. INTRODUCTIONTime-dependent density functional theory ͑TDDFT͒ developed by Runge and Gross 1 makes it possible to describe the dynamic properties of interacting many-particle systems in an exact manner. 1-4 Dhara and Ghosh 5 and Ghosh and Dhara 6 showed that the Runge-Gross theorem could be extended to systems that are subjected to general timedependent electromagnetic fields ͑see also Ref. 7͒. The method has proven to be an accurate tool in the study of electronic response properties. 3,8,9 In this paper, we study infinite systems for which we use time-dependent currentdensity-functional theory ͑TDCDFT͒. 7,[10][11][12] In this approach, the electron density of TDDFT is substituted by the electron current density as the fundamental quantity. There are mainly three reasons to use TDCDFT instead of ordinary TDDFT. The first reason is related to the use of periodic boundary conditions, which provide an efficient way to describe infinite systems but that artificially remove the effects of density changes at the surface. 13 For example, when a system is perturbed by an electric field there will be a macroscopic response of the system and a current will be flowing through the interior with a n...

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Ultranonlocality in Time-Dependent Current-Density-Functional Theory: Application to Conjugated Polymers

Cited by 230 publications

References 25 publications

Assessment of a Middle-Range Hybrid Functional

Assessment of a Middle-Range Hybrid Functional

Lattice dynamics of polyaniline and poly(p-pyridyl vinyline): First-principles determination

Analysis of the Vignale-Kohn current functional in the calculation of the optical spectra of semiconductors

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