Semiempirical calculation of van der Waals coefficients for alkali-metal and alkaline-earth-metal atoms

Mitroy, Jim; Bromley, Michael W. J.

doi:10.1103/physreva.68.052714

Cited by 161 publications

(116 citation statements)

References 64 publications

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“…51,52 The damping function f damp prevents the nonadditive energy from exploding at short range and was chosen to have a product form, f damp ͑r 12 , r 23 , r 13 ͒ = f͑r 12 ͒f͑r 23 ͒f͑r 13 ͒, where …”

Section: ͑5͒mentioning

confidence: 99%

Potential energy surface for spin-polarized rubidium trimer

Soldán

2010

The Journal of Chemical Physics

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Potential energy surface for the lowest quartet state of the rubidium trimer is constructed, making use of the many-body decomposition. Interaction energies are calculated using the coupled-clusters method and interpolated using the reciprocal-power reproducing kernel Hilbert space interpolation method. Both the two-body and three-body nonadditive parts are extrapolated to exhibit the correct long-range behavior. Consequences for the low-energy scattering are briefly discussed.

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Section: ͑5͒mentioning

confidence: 99%

Potential energy surface for spin-polarized rubidium trimer

Soldán

2010

The Journal of Chemical Physics

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“…A semiempirical polarization potential was included and tuned to reproduce the correct 2p 1/2 and 2p 3/2 energies and the transition matrix elements. The method is very much a relativistic analog of the nonrelativistic calculations used to compute the CICP dynamic polarizability [9,25,34]. Using Eq.…”

Section: Li(2s) Tune-out Wavelengthmentioning

confidence: 99%

Dynamic Stark shift of the7Li(2s→3s) transition

et al. 2013

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“…First, we demand recovery of the correct zero-frequency limit α l ð0Þ. Second, we demand recovery of the correct high-frequency (u → ∞) limit (29,32),…”

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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Semiempirical calculation of van der Waals coefficients for alkali-metal and alkaline-earth-metal atoms

Cited by 161 publications

References 64 publications

Potential energy surface for spin-polarized rubidium trimer

Potential energy surface for spin-polarized rubidium trimer

Dynamic Stark shift of the7Li(2s→3s) transition

Accurate van der Waals coefficients from density functional theory

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