<i>Ab</i> <i>initio</i> dispersion coefficients for interactions involving rare-gas atoms

Thakkar, Ajit J.; Hettema, Hinne; Wormer, Paul E. S.

doi:10.1063/1.463012

Cited by 138 publications

(88 citation statements)

References 38 publications

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“…Finally, we evaluate C 8 and C 10 of 78 diverse atom-atom-pair interactions by substituting the model dynamic multipole polarizabilities Eqs. 6, [8], and [9], into the exact expression [2]. (The explicit expressions for C 6 , C 8 , and C 10 , and detailed numerical results, are given in the SI Text).…”

Section: Nonempirical Model For the Dynamic Multipole Polarizabilitymentioning

confidence: 99%

Accurate van der Waals coefficients from density functional theory

Tao

Perdew

Ruzsinszky

2011

Proc. Natl. Acad. Sci. U.S.A.

104

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The van der Waals interaction is a weak, long-range correlation, arising from quantum electronic charge fluctuations. This interaction affects many properties of materials. A simple and yet accurate estimate of this effect will facilitate computer simulation of complex molecular materials and drug design. Here we develop a fast approach for accurate evaluation of dynamic multipole polarizabilities and van der Waals (vdW) coefficients of all orders from the electron density and static multipole polarizabilities of each atom or other spherical object, without empirical fitting. Our dynamic polarizabilities (dipole, quadrupole, octupole, etc.) are exact in the zero-and high-frequency limits, and exact at all frequencies for a metallic sphere of uniform density. Our theory predicts dynamic multipole polarizabilities in excellent agreement with more expensive many-body methods, and yields therefrom vdW coefficients C 6 , C 8 , C 10 for atom pairs with a mean absolute relative error of only 3%.T he van der Waals interaction (1) is a long-range attraction between chemical species, arising from instantaneous charge fluctuations on each. This interaction is present even when there is no chemical bond, and even when each species has no permanent multipole moment. Its significance first came to light when van der Waals (vdW) (2) formulated the equation of state for real gases and liquids in 1873 by taking this correlation effect into consideration. The vdW interaction is much weaker in strength than a normal chemical bond, but it has important effects on the properties of materials (3). For example, it is responsible for many phenomena such as sublimation of iodine, naphthalene, dry ice, and other organic molecules, high interlayer mobility of graphite, foldings of long biomolecular chains such as DNA, RNA, proteins, polymers, etc. The vdW interaction has been extensively studied (4, 5) on account of its ubiquity and importance for soft matter relevant to human activity. Many theoretical methods, including CI (6, 7) (configuration interaction), MBPT (8) (manybody perturbation theory), coupled cluster (9) methods, or their combinations such as CI+MBPT (10, 11), have been developed to estimate this effect. These methods are highly accurate (within about 1%) but computationally expensive. A cheap but usefully accurate method is density functional theory (12) (DFT). While this theory has achieved a high level of sophistication and has become the mainstream electronic structure theory, it often fails in practice to describe vdW systems, because the long-range part of the vdW interaction is absent in commonly used DFT approximations [e.g.,[13][14][15]].In the large separation limit of two spherically symmetric interacting densities A and B, second-order perturbation theory yields the (nonretarded) potential energy E vdW , which can be expressed as a power series (16),where R is the separation between centers, C 6 describes the instantaneous dipole-dipole interaction, C 8 the dipole-quadrupole interaction, and C 10 the quadrupol...

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Section: Nonempirical Model For the Dynamic Multipole Polarizabilitymentioning

confidence: 99%

Accurate van der Waals coefficients from density functional theory

Tao

Perdew

Ruzsinszky

2011

Proc. Natl. Acad. Sci. U.S.A.

104

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“…Thakkar et al proposed a simpler but less accurate empirical formula relating C 8 and C 10 to C 6 for atom pairs. 33 Some attempts 26,34 were made to account for the higher-order (C 8 ) contribution in terms of C 6 for molecular systems, but it is not equivalent to the corresponding coefficient in Eq. (1).…”

mentioning

confidence: 99%

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

Tao

Rappe

2016

The Journal of Chemical Physics

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Due to the absence of the long-range van der Waals (vdW) interaction, conventional density functional theory (DFT) often fails in the description of molecular complexes and solids. In recent years, considerable progress has been made in the development of the vdW correction. However, the vdW correction based on the leading-order coefficient C6 alone can only achieve limited accuracy, while accurate modeling of higher-order coefficients remains a formidable task, due to the strong non-additivity effect. Here, we apply a model dynamic multipole polarizability within a modified single-frequency approximation to calculate C8 and C10 between small molecules. We find that the higher-order vdW coefficients from this model can achieve remarkable accuracy, with mean absolute relative deviations of 5% for C8 and 7% for C10. Inclusion of accurate higher-order contributions in the vdW correction will effectively enhance the predictive power of DFT in condensed matter physics and quantum chemistry.

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“…26,27 The agreement with the latest ab initio potentials over six orders of magnitude is better than 20% (H 2 and He 2 ) or in the case of H-He comparable to the differences in the available ab initio calculations. The present calculations are based on the two well parameters R e and D e taken from the most accurate recent results of the ab initio theory.…”

Section: Discussionmentioning

confidence: 75%

Communication: A simple full range analytical potential for H2b3∑u+, H–He 2∑+, and He21∑g+

Warnecke

Tang

Toennies

2015

The Journal of Chemical Physics

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The Tang-Toennies potential for the weakly interacting systems H 2 b 3 Σ + u , H-He 2 Σ + , and He 2 1 Σ + g is extended down to the united atom limit of vanishing internuclear distance. A simple analytic expression connects the united atom limiting potential with the Tang-Toennies potential in the well region. The new potential model is compared with the most recent ab initio calculations for all three systems. The agreement is better than 20% (H 2 and He 2 ) or comparable with the differences in the available ab initio calculations (H-He) over six orders of magnitude corresponding to the entire range of internuclear distances. C 2015 AIP Publishing LLC.[http://dx

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Ab initio dispersion coefficients for interactions involving rare-gas atoms

Cited by 138 publications

References 38 publications

Accurate van der Waals coefficients from density functional theory

Accurate van der Waals coefficients from density functional theory

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

Communication: A simple full range analytical potential for H2b3∑u+, H–He 2∑+, and He21∑g+

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