Communication: Accurate higher-order van der Waals coefficients between molecules from a model dynamic multipole polarizability

Tao, Jianmin; Rappe, Andrew M.

doi:10.1063/1.4940397

Cited by 27 publications

(37 citation statements)

References 59 publications

(42 reference statements)

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“…Compared to the original SFA, the MSFA yields the dynamic dipole polarizability in better agreement with the TDHF values for fullerene C 60 , in particular in the important low-frequency region. This accuracy is consistent with a recent application to diatomics and small molecules 50 , where it was found that the MSFA yields accurate vdW coefficients, with a MARE of 6% for C 6 , 5% for C 8 , and 7% for C 10 . This small relative error difference is largely due to the fact that the electron density on the surface of fullerenes and in sodium clusters is not rapidly varying, but it is for small molecules, in particular diatomics.…”

Section: Discussionsupporting

confidence: 72%

“…As a result, the errors of the two models are nearly size-independent, as confirmed by vdW coefficients for nanoclusters 49,50,52 . More recently, one of the present authors (JT) 50 applied the solid-sphere model to calculate both the leading-order and higherorder vdW coefficients between small molecules, within the modified single-frequency approximation (see discussion below). The results are in very good agreement with expensive TDMP2 or TDHF calculations, with mean absolute relative errors of 6% for C 6 , 5% for C 8 , and 7% for C 10 .…”

Section: Introductionmentioning

confidence: 70%

“…In recent years, several methods beyond atom pairwisebased models for the calculation of vdW coefficients have been developed [40][41][42][43][44][45][46][47][48][49][50][51] . A common feature of these beyondatom pairwise-based methods is that they treat the electrons to be distributed over the whole system, rather than partition them in terms of atoms in a molecule.…”

Section: Introductionmentioning

confidence: 99%

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Accurate van der Waals coefficients between fullerenes and fullerene-alkali atoms and clusters: Modified single-frequency approximation

Tao

Tian

et al. 2016

Phys. Rev. B

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Long-range van der Waals (vdW) interaction is critically important for intermolecular interactions in molecular complexes and solids. However, accurate modeling of vdW coefficients presents a great challenge for nanostructures, in particular for fullerene clusters, which have huge vdW coefficients but also display very strong nonadditivity. In this work, we calculate the coefficients between fullerenes, fullerene and sodium clusters, and fullerene and alkali atoms, with the hollow-sphere model within the modified single-frequency approximation (MSFA). In the MSFA, we assume that the electron density is uniform in a molecule, and that only valence electrons in the outmost subshell of atoms contribute. The input to the model is the static multipole polarizability, which provides a sharp cutoff for the plasmon contribution outside the effective van der Waals radius. We find that the model can generate C6 in excellent agreement with expensive wave function-based ab initio calculations, with a mean absolute relative error of only 3%, without suffering size-dependent error. We show that the nonadditivities of the coefficients C6 between fullerenes and C60 and sodium clusters Nan revealed by the model agree remarkably well with those based on the accurate reference values. The great flexibility, simplicity, and high accuracy make the model particularly suitable for the study of the nonadditivity of vdW coefficients between nanostructures, advancing the development of better vdW corrections.

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Section: Discussionsupporting

confidence: 72%

Section: Introductionmentioning

confidence: 70%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Accurate van der Waals coefficients between fullerenes and fullerene-alkali atoms and clusters: Modified single-frequency approximation

Tao

Tian

et al. 2016

Phys. Rev. B

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“…However, semilocal DFT often fails to describe this process, because the long-range vdW interaction is missing in semilocal DFT. Many attempts 25,[41][42][43][44][45][46][47][48][49][50][51][52][53][54] have been made to capture this long-range part, such as nonlocal vdW-DF functional 41 and density functional dispersion correction 55,56 . It has been shown that with a proper dispersion correction, the performance of ordinary DFT methods can be significantly improved 26 .…”

Section: Vdw Coefficientsmentioning

confidence: 99%

Frequency-dependent dielectric function of semiconductors with application to physisorption

2017

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The dielectric function is one of the most important quantities that describes the electrical and optical properties of solids. Accurate modeling of the frequency-dependent dielectric function has great significance in the study of the long-range van der Waals (vdW) interaction for solids and adsorption. In this work, we calculate the frequency-dependent dielectric functions of semiconductors and insulators using the GW method with and without exciton effects, as well as efficient semilocal density functional theory (DFT), and compare these calculations with a model frequency-dependent dielectric function. We find that for semiconductors with moderate band gaps, the model dielectric functions, GW values, and DFT calculations all agree well with each other. However, for insulators with strong exciton effects, the model dielectric functions have a better agreement with accurate GW values than the DFT calculations, particularly in high-frequency region. To understand this, we repeat the DFT calculations with scissors correction, by shifting DFT Kohn-Sham energy gap to match the experimental band gap. We find that scissors correction only moderately improves the DFT dielectric function in low-frequency region. Based on the dielectric functions calculated with different methods, we make a comparative study by applying these dielectric functions to calculate the vdW coefficients (C 3 and C 5 ) for adsorption of rare-gas atoms on a variety of surfaces. We find that the vdW coefficients obtained with the nearly-free electron gas-based model dielectric function agree quite well with those obtained from the GW dielectric function, in particular for adsorption on semiconductors, leading to an overall error of less than 7% for C 3 and 5% for C 5 . This demonstrates the reliability of the model dielectric function for the study of physisorption.2

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“…The first property is very important for surface energy calculations, while the second is helpful in capturing the van der Waals interactions, [72][73][74][75][76][77][78][79] as demonstrated by the excellent performance of the TM functional for lattice constants (Table II) and cohesive energies (Table V). Recently, we have also assessed 80 the TM functional on diverse molecular properties and found that it has a similarly good accuracy for atoms and molecules as for solids.…”

Section: Discussionmentioning

confidence: 99%

Assessment of the Tao-Mo nonempirical semilocal density functional in applications to solids and surfaces

Car

Staroverov

et al. 2017

Phys. Rev. B

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Recently, Tao and Mo developed a new semilocal exchange-correlation density functional. The exchange part of this functional is derived from a density matrix expansion corrected to reproduce the fourth-order gradient expansion in the slowly-varying-density limit, while the correlation part is based on the TPSS correlation functional with a modification for the low-density limit. In the present work, the Tao-Mo functional is assessed by computing various properties of solids and jellium surfaces. This includes 22 lattice constants and bulk moduli, 30 band gaps, 7 cohesive energies, and jellium surface exchange and correlation energies for the density parameter r s in the range from 2 to 3 bohrs. Our calculations show that the Tao-Mo meta-generalized gradient approximation can yield consistently high accuracy for most properties considered here, with mean absolute errors of 0.025 Å for lattice constants, 7.0 GPa for bulk moduli, 0.08 eV/atom for cohesive energies, and 35 erg/cm 2 for surface exchange-correlation energies.The mean absolute error in band gaps is larger than that of TPSS, but slightly smaller than the errors of LSDA, PBE, and revTPSS. However, band gaps are still underestimated, particularly for large-gap semiconductors, compared to the HSE06 nonlocal screened hybrid functional.

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Communication: Accurate higher-order van der Waals coefficients between molecules from a model dynamic multipole polarizability

Cited by 27 publications

References 59 publications

Accurate van der Waals coefficients between fullerenes and fullerene-alkali atoms and clusters: Modified single-frequency approximation

Accurate van der Waals coefficients between fullerenes and fullerene-alkali atoms and clusters: Modified single-frequency approximation

Frequency-dependent dielectric function of semiconductors with application to physisorption

Assessment of the Tao-Mo nonempirical semilocal density functional in applications to solids and surfaces

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