# Short distance relativistic atom-atom forcesContribution for third issue of the Bulletin of the Asia Pacific Center for Theoretical Physics, Seoul, Korea.

About fifty years ago two important papers appeared describing novel interactions. One, by Casimir, discussed the case of two interacting walls  and the other, by Casimir and Polder, considered the interactions between an atom and a wall and between two atoms . The history and some of the many interesting aspects of these interactions, their derivations, and their importance in field theory and atomic and molecular physics are summarized elsewhere . Indeed, recent experiments give strong evidence of the reality of both the atom-wall  and the wall-wall interactions  predicted in those two papers.

Here I will focus on the connection between the QED result of Casimir and Polder and other results for relativistic atom-atom interactions at short distances of the order of, say, $`20a_0`$. The interaction between an electron and an ion will also be considered. For typical atomic systems these relativistic effects are very small corrections to the non-relativistic potentials arising from the van der Waals and Coulomb interactions for, respectively, the atom-atom interaction and the electron-ion interaction.

Casimir and Polder used QED and old-fashioned perturbation theory and their result was subsequently duplicated by other authors with different methods, cf. . One way to write their result for the interaction potential $`V(R)`$ between two spherically symmetric atoms separated by a distance $`R`$ is as a one-dimensional integral

$$V(R)=\frac{1}{\pi R^6}_0^{\mathrm{}}𝑑\omega \mathrm{exp}(2\alpha \omega R)[\alpha _d(i\omega )]^2P(\omega \alpha R),$$
(1)   
with $`P(x)=x^4+2x^3+5x^2+6x+3`$ and $`\alpha `$ the fine structure constant. Atomic units $`\mathrm{}=m=e=1`$ are used throughout and in these units $`c=1/\alpha `$. The function $`\alpha _d(i\omega )`$ is the dynamic electric dipole polarizability at imaginary frequency,

$$\alpha _d(i\omega )=\underset{u}{}f_u/[(E_uE_0)^2+\omega ^2],$$
(2)   
where $`f_u`$ is the oscillator strength of state $`u`$ and $`E_uE_0`$ is the transition frequency between the states $`u`$ and $`0`$, with $`0`$ denoting the ground state of the atom, and the summation in (2) includes an integration over continuum states. The function $`\alpha _d(i\omega )`$ is a smooth function of $`\omega `$ with no singularities. The limit of $`V(R)`$ for asymptotically large separations of the atoms can be obtained from the Casimir-Polder integral (1) yielding

$$V(R)\frac{23}{4\pi }\frac{[\alpha _d(0)]^2}{\alpha R^7},R\mathrm{}.$$
(3)   
What about the limit for small $`R`$? The result is

$$V(R)\frac{3}{\pi R^6}_0^{\mathrm{}}𝑑\omega [\alpha _d(i\omega )]^2,R137,$$
(4)   
and upon integration (4) yields

$$V(R)C_6/R^6,$$
(5)   
where $`C_6`$ is the van der Waals constant expressed as a double sum over oscillator strengths and the correct form of the atom-atom interaction at short distances (say $`20a_0`$) is reproduced. The van der Waals constant is of vast importance for all sorts of molecular spectroscopic and atomic collision problems, of course. The result for two H atoms is $`C_6=\mathrm{6.499\hspace{0.17em}026\hspace{0.17em}705}\mathrm{}`$ and for studies of atomic collisions at ultracold temperatures $`C_6`$ plays a crucial role in characterizing the interactions . So it is nice to see QED connect nicely with non-relativistic molecular quantum mechanics. What is the next correction?

If one more term is retained in the small $`R`$ expansion then 

$$V(R)=\frac{C_6}{R^6}+\alpha ^2\frac{W_4}{R^4}+𝒪(\alpha ^3/R^3)$$
(6)   
where

$$W_4=\frac{1}{\pi }_0^{\mathrm{}}𝑑\omega \omega ^2[\alpha _d(i\omega )]^2.$$
(7)   
By integrating (7), the coefficient $`W_4`$ can be expressed as a double sum over oscillator strengths and it was evaluated for a small number of diatomic systems using various approximations, both semi-empirical  and computational . The result for two H atoms is $`W_4=\mathrm{0.462\hspace{0.17em}807}`$. The derivations above assume that the two atoms are well-separated and accordingly do not include considerations involving electron exchange.

How do the results above connect with results from the Breit-Pauli approximation to the Dirac equation? The van der Waals potential was shown above to be the short range limit of the QED result; yet it is also the long-range limit of the molecular interaction potential. The full power of quantum-chemical methods (recognized in the 1998 Nobel Prize in Chemistry) enables, at least in principle, calculation of the molecular potential by solution of the nonrelativistic Schrödinger equation. Relativistic effects are treated using perturbation theory on the terms in the Breit-Pauli Hamiltonian (or for molecules containing high-$`Z`$ atoms by solution of the Dirac equation.) The connection to (6) was given by Power and Zienau  who showed using perturbation theory that the matrix element of the orbit-orbit interaction $`H_{\mathrm{oo}}`$ reproduces the second term in (6) as $`R`$ increases,

$$\stackrel{~}{0}|H_{\mathrm{oo}}|\stackrel{~}{0}\alpha ^2\frac{W_4}{R^4},RR_0,$$
(8)   
where $`R_0`$ is of order, say, $`10`$ to $`20a_0`$ and $`|\stackrel{~}{0}`$ is the molecular ground electronic state wave function. Therefore there is a smooth connection between the relativistic and Casimir-Polder results.

This relativistic $`R^4`$ term might be studied by incorporating it into theoretical calculations of collisions of ultra-cold atoms, particularly for H-H, H-Li, and Li-Li where high precision determinations of the molecular potentials are possible. There are of course additional subtle effects to be accounted for such as deviations from the Born-Oppenheimer approximation through isotope effects and nonadiabatic terms (nonlocal terms arising from the action of the nuclear kinetic energy operator on the electronic wave function) and additional relativistic terms like the $`p^4`$ and Darwin terms, for example, but these are unrelated to the Casimir-Polder result.

The Casimir-Polder-type interaction between an electron and an ion is closely related to that of the atom-atom interaction (3). Kelsey and Spruch  exhibited the result for asymptotic separations,

$$U(R)\frac{11}{4\pi }\frac{\alpha \alpha _d(0)}{R^5},R\mathrm{},$$
(9)   
where $`R`$ now denotes the electron-ion distance. They obtained (9) using QED and old-fashioned perturbation theory and they considered the possibility of measurement of this potential through spectroscopy of the Rydberg states of atoms. Later, the integral form of $`U(R)`$, analogous to (1), was obtained  yielding an expression not particularly more complicated than (1) and which can be obtained essentially by replacing the polarizability $`\alpha _d(i\omega )`$ of one of the atoms by the quantity $`1/\omega ^2`$, which is an excellent approximation to the polarizability of the weakly bound electron . (Some care is required, however, due to the additional Coulomb interaction present for the ion-electron case, see  for details.) The limit of the electron-ion “Casimir-Polder” potential for small $`R`$ for an electron interacting with an ion (of net charge $`Z1`$) is 

$$U(R)=\frac{\alpha ^2}{Z^2}\frac{1}{R^4}+𝒪(\alpha ^3/R^3),R137/Z^2.$$
(10)   
Similarly to the atom-atom case, the relativistic $`R^4`$ term in the ion-electron interaction was derived alternatively using $`H_{\mathrm{oo}}`$ with perturbation theory on the non-relativistic wave function of the Rydberg atom  providing a connection to the QED result (10). This term is a small correction to the much larger Coulomb interaction between the two charged particles, but nevertheless, through much theoretical work by Drachman, Drake, and others , there is definitive evidence for the first term of (10) from a long series of careful measurements of energies of Rydberg states of the helium atom by Lundeen and collaborators . At present the asymptotic part of $`U(R)`$, (9), has not been measured and Hessels and collaborators  conclude from their measurements that there is, in fact, no experimental evidence for deviations from (10). Additional experiments are in progress  and it will be interesting to see if the ion-electron Casimir effect will be verified. From a theoretical point of view there are interesting connections at short  and long distance between the order $`𝒪(\alpha ^3/R^3)`$ QED corrections in (6) and (10).

This work was supported in part by the National Science Foundation through a grant for the Institute for Theoretical Atomic and Molecular Physics at the Smithsonian Astrophysical Observatory and Harvard University.