Erratum: “Assessment of conventional density functional schemes for computing the polarizabilities and hyperpolarizabilities of conjugated oligomers: An <i>ab initio</i> investigation of polyacetylene chains” [J. Chem. Phys. <b>109</b>, 10489 (1998)]

Champagne, Benoı̂t; Perpète, Éric A.; Gisbergen, S.J.A. van; Baerends, E. J.; Snijders, J.G.; Soubra‐Ghaoui, Chirine; Robins, Kathleen A.

doi:10.1063/1.479106

Cited by 116 publications

(124 citation statements)

References 0 publications

Supporting

Mentioning

117

Contrasting

Order By: Relevance

“…The calculated ⌬␣ for DPD deviates considerably from the experimental value. This overestimate for long conjugated system has also been found for ground state polarizabilities of polyenes as reported by Champagne et al 41 This incorrect behavior for long ͑conjugated͒ molecules is related to the shortsightedness of present XC potentials which mainly feel the local density and are relatively insensitive to polarization charges induced by an external electric field at the chain ends. 41 For short oligomers this problem does not arise.…”

Section: Singlet B U Excitonsmentioning

confidence: 76%

Excited state polarizabilities of conjugated molecules calculated using time dependent density functional theory

Grozema

Telesca

Jonkman

et al. 2001

The Journal of Chemical Physics

100

View full text Add to dashboard Cite

In this paper, time-dependent density functional theory ͑TDDFT͒ calculations of excited state polarizabilities of conjugated molecules are presented. The increase in polarizability upon excitation was obtained by evaluating the dependence of the excitation energy on an applied static electric field. The excitation energy was found to vary quadratically with the field strength. The excess polarizabilities obtained for singlet excited states are in reasonable agreement with the experimental results for the shorter oligomers, particularly if the experimental uncertainties are considered. For longer oligomers the excess polarizability is considerably overestimated, similar to DFT calculations of ground state polarizabilities. Excess polarizabilities of triplet states were found to be smaller than those for the corresponding singlet state, which agrees with experimental results that are available for triplet polarizabilities. Negative polarizabilities are obtained for the lowest singlet A g states of longer oligomers. The polarizability of the lowest B u and A g excited states of the conjugated molecules studied here are determined mainly by the interaction between these two states. Upon application of a static electric field a quadratic Stark effect is observed in which the lower B u state has a positive excess polarizability and the upper A g state exhibits a decrease in polarizability upon excitation. All results are explained in terms of a sum-over-states description for the polarizability.

show abstract

Section: Singlet B U Excitonsmentioning

confidence: 76%

Excited state polarizabilities of conjugated molecules calculated using time dependent density functional theory

Grozema

Telesca

Jonkman

et al. 2001

The Journal of Chemical Physics

100

View full text Add to dashboard Cite

show abstract

“…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 simple HF theory provides results which are in qualitative agreement with the more advanced [16] Møller-Plesset (MP) and coupled cluster calculations. The problem with the LDA and GGA xc potentials can be clarified by comparing the LDA and HF results for a and g of PA chains ͑C 2n H 2n12 ͒, with a varying number of unit cells n. This is done in Fig.…”

mentioning

confidence: 99%

mentioning

confidence: 99%

“…[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.…”

mentioning

confidence: 99%

“…[18]. Our analysis started with the observation [6] that GGA potentials, or the asymptotically correct (behaving as 21͞r for large r) LB94 xc potential [19], do not improve upon LDA (thus showing that the problem is unrelated to the slight LDA overestimation for small molecules [20]). We then constructed, for linear polyyne and hydrogen chains, xc potentials reproducing HF and CI densities in the presence or absence of an external field.…”

mentioning

confidence: 99%

See 2 more Smart Citations

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

et al. 1999

View full text Add to dashboard Cite

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...

show abstract

Coupled‐Cluster Calculations for Large Molecular and Extended Systems

Kowalski¹,

Hammond²,

Jong³

et al. 2011

Computational Methods for Large Systems

View full text Add to dashboard Cite

Erratum: “Assessment of conventional density functional schemes for computing the polarizabilities and hyperpolarizabilities of conjugated oligomers: An ab initio investigation of polyacetylene chains” [J. Chem. Phys. 109, 10489 (1998)]

Cited by 116 publications

References 0 publications

Excited state polarizabilities of conjugated molecules calculated using time dependent density functional theory

Excited state polarizabilities of conjugated molecules calculated using time dependent density functional theory

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

Coupled‐Cluster Calculations for Large Molecular and Extended Systems

Contact Info

Product

Resources

About