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arXiv:physics/0510277 · Physical Review A

Relativistic corrections to the long-range interaction between closed-shell atoms

Krzysztof Pachucki

Published Dec 14, 2005• 20 citations
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Abstract

The complete $O({\ensuremath{\alpha}}^{2})$ correction to the long-range interaction between neutral closed-shell atoms is obtained, the relation to the asymptotic expansion of the known short-range interaction at the atomic scale is presented and a general interaction potential that is valid in the whole range of the interatomic distances is constructed.

DOI
10.1103/physreva.72.062706

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The complete O(\ensuremathα2)O({\ensuremath{\alpha}}^{2})O(\ensuremathα2) correction to the long-range interaction between neutral closed-shell atoms is obtained, the relation to the asymptotic expansion of the known short-range interaction at the atomic scale is presented and a general interaction potential that is valid in the whole range of the interatomic distances is constructed.
The long-range asymptotic form of the interaction potential surface for three neutral alkali-metal atoms in their ground states may be expressed as an expansion in inverse powers of inter-nuclear distances. The first leading powers are proportional to the dispersion coefficients for pairwise atomic interactions. They are followed by a term responsible for a three body dipole interaction. The authors results consist in evaluation of the three body dipole interaction coefficient between three alkali-metal atoms. The generalization to long-range n atom interaction terms will be discussed qualitatively.
The term long-range interactions refers to electrostatic and magnetostatic potential energies between atoms and molecules with mutual distances ranging from a few tens to a few hundreds of Bohr radii. The energies involved are much smaller than the usual chemical bond energies. However, they are comparable with the typical kinetic energies of particles in an ultracold gas (T ≪ 1 K), so that the long-range interactions play a central role in its dynamics. The progress of research devoted to ultracold gases sheds a new light on the well-established topic of long-range interactions, because (i) the interacting atoms and molecules can be prepared in a well-defined quantum (electronic, vibrational, rotational, fine or hyperfine), ground or excited level; and (ii) long-range interactions can be tailored at will using external electromagnetic fields. In this chapter, we present the essential concepts and mathematical relations to calculate long-range potential energies. We start by deriving the multipolar expansion of the electrostatic interaction energy between classical charge distributions, both in Cartesian coordinates for pedagogical purpose, and in spherical coordinates for practical use. Then we combine multipolar expansion and quantum perturbation theory, to obtain the general first- and second-order energy corrections, including the well-known van der Waals energy. We consider two central examples in the current context of ultracold gases: (i) a pair of alkali metal atoms and (ii) a pair of alkali metal heteronuclear diatomic molecules in the presence of an electric field. We highlight the key role of the total angular momenta of the interacting particles and of the complex, irrespective of their electronic or nuclear, orbital or spin nature.
The term "long-range interactions" refers to electrostatic and magnetostatic potential energies between atoms and molecules with mutual distances ranging from a few tens to a few hundreds Bohr radii. The involved energies are much smaller than the usual chemical bond energies. However, they are comparable with the typical kinetic energies of particles in an ultracold gas (T≪1KT\ll 1KT≪1K), so that the long-range interactions play a central role in its dynamics. The progress of research devoted to ultracold gases shed a new light on the well-established topic of long-range interactions, because: (i) the interacting atoms and molecules can be prepared in a well-defined quantum (electronic, vibrational, rotational, fine or hyper-fine), ground or excited level; and (ii) long-range interactions can be tailored at will using external electromagnetic fields. In this chapter, we present the essential concepts and mathematical relations to calculate long-range potential energies. We start with deriving the multipolar expansion of the electrostatic interaction energy between classical charge distributions, both in Cartesian coordinates for pedagogical purpose, and in spherical coordinates for practical use. Then we combine multipolar expansion and quantum perturbation theory, to obtain the general first- and second-order energy corrections, including the well-known van der Waals energy. We consider two central examples in the current context of ultracold gases: (i) a pair of alkali-metal atoms and (ii) a pair of alkali-metal heteronuclear diatomic molecules submitted to an electric field. We highlight the key role of the total angular momenta of the interacting particles and of the complex, irrespective of their electronic or nuclear, orbital or spin nature.
We describe a method for evaluating analytical long-range contributions to scattering lengths for some potentials used in atomic physics. We assume that an interaction potential between colliding particles consists of two parts. The form of a short-range component, vanishing beyond some distance from the origin (a core radius), need not be given. Instead, we assume that a set of short-range scattering lengths due to that part of the interaction is known. A long-range tail of the potential is chosen to be an inverse power potential, a superposition of two inverse power potentials with suitably chosen exponents or the Lent potential. For these three classes of long-range interactions a radial Schrodinger equation at zero energy may be solved analytically with solutions expressed in terms of the Bessel, Whittaker and Legendre functions, respectively. We utilize this fact and derive exact analytical formulae for the scattering lengths. The expressions depend on the short-range scattering lengths, the core radius and parameters characterizing the long-range part of the interaction. Cases when the long-range potential (or its part) may be treated as a perturbation are also discussed and formulae for scattering lengths linear in strengths of the perturbing potentials are given. It is shown that for some combination of the orbital angular momentum quantum number and an exponent of the leading term of the potential the derived formulae, exact or approximate, take very simple forms and contain only polynomial and trigonometric functions. The expressions obtained in this paper are applicable to scattering of charged particles by neutral targets and to collisions between neutrals. The results are illustrated by accelerating convergence of scattering lengths computed for e - -Xe and Cs-Cs systems.
Neutral atoms interact through a van der Waals potential which asymptotically falls off as ${r}^{\ensuremath{-}6}$. In ultracold gases, this interaction can be described to a good approximation by the atom-atom scattering length. However, corrections arise that depend on the characteristic length of the van der Waals potential. We parametrize these corrections by analyzing the energies of two- and few-atom systems under external harmonic confinement, obtained by numerically and analytically solving the Schr\"odinger equation. We generalize our results to particles interacting through a longer-ranged potential which asymptotically falls off as ${r}^{\ensuremath{-}4}$.
At long distances, interactions between neutral ground-state atoms can be described by the van der Waals potential. In the ultracold regime, atom-atom scattering is dominated by sss-waves phase shifts given by an effective range expansion in terms of the scattering length ${\ensuremath{\alpha}}_{0}$ and the effective range r0{r}_{0}r0​. We show that while the scattering length cannot be predicted for these potentials, the effective range is given by the universal low-energy theorem ${r}_{0}=A+B/{\ensuremath{\alpha}}_{0}+C/{\ensuremath{\alpha}}_{0}^{2}$, where AAA, BBB, and CCC depend on the dispersion coefficients Cn{C}_{n}Cn​ and the reduced diatom mass. We confront this formula to about 100 determinations of r0{r}_{0}r0​ and ${\ensuremath{\alpha}}_{0}$ and show why the result is dominated by the leading dispersion coefficient C6{C}_{6}C6​. Universality and scaling extend much beyond naive dimensional analysis estimates.