The interaction of two excited hydrogen atoms in metastable states constitutes a theoretically interesting problem because of the quasidegenerate
2P1/2 levels that are removed from the
2S states only by the Lamb shift. The total Hamiltonian of the system is composed of the van der Waals Hamiltonian, the Lamb shift, and the hyperfine effects. The van der Waals shift becomes commensurate with the $2S\ensuremath{-}2{P}_{3/2}$ fine-structure splitting only for close approach (
R<100a0, where
a0 is the Bohr radius) and one may thus restrict the discussion to the levels with
n=2 and
J=1/2 to a good approximation. Because each
S or
P state splits into an
F=1 triplet and an
F=0 hyperfine singlet (eight states for each atom), the Hamiltonian matrix a priori is of dimension 64. A careful analysis of the symmetries of the the problem allows one to reduce the dimensionality of the most involved irreducible submatrix to 12. We determine the Hamiltonian matrices and the leading-order van der Waals shifts for states that are degenerate under the action of the unperturbed Hamiltonian (Lamb shift plus hyperfine structure). The leading first- and second-order van der Waals shifts lead to interaction energies proportional to
1/R3 and
1/R6 and are evaluated within the hyperfine manifolds. When both atoms are metastable
2S states, we find an interaction energy of order ${E}_{h}\ensuremath{\chi}{({a}_{0}/R)}^{6}$, where
Eh and
L are the Hartree and Lamb shift energies, respectively, and $\ensuremath{\chi}={E}_{h}/\mathcal{L}\ensuremath{\approx}6.22\ifmmode\times\else\texttimes\fi{}{10}^{6}$ is their ratio.
With the use of second-order perturbation theory in the long-range interatomic interaction for the degenerate states of two Rydberg atoms we have obtained a general formula for the dependence of atomic interaction energy on the interatomic distance R in the presence of the Förster resonance. Inside of the ‘Förster sphere’ ( R < R F ) this dependence transforms to the formula for electric dipole interaction energy Δ E d − d = C 3 / R 3 and for R > R F it transforms to the formula for the van der Waals interaction energy Δ E VdW = − C 6 / R 6 . The van der Waals constant C 6 is represented as an expansion in terms of irreducible components which define the dependence on the interatomic axis orientation relative to the quantisation axis of projections M of the total angular momentum J . The numerical values of the irreducible components of tensor C 6 were calculated for rubidium atoms in the same Rydberg states | nlJM 〉 with large quantum numbers n . We present the calculated resonance interaction energy of two rubidium atoms in the states |43D 5/2 M 〉, whose total energy exceeds by only 8 MHz the total energy of one of the atoms in the state |45P 3/2 M 〉 and of the other in the state |41F 7/2 M 〉.
We theoretically investigate long-range interactions between an excited
L-state He atom and two identical
S-state He atoms for the cases of the three atoms all in spin-singlet states or all in spin-triplet states, denoted by He(${n}_{0}^{\ensuremath{\lambda}}S$)-He(${n}_{0}^{\ensuremath{\lambda}}S$)-He(${n}_{0}^{\ensuremath{'}\ensuremath{\lambda}}L$), with
n0 and ${n}_{0}^{\ensuremath{'}}$ principal quantum numbers, $\ensuremath{\lambda}=1$ or 3 the spin multiplicity, and
L the orbital angular momentum of a He atom. Using degenerate perturbation theory for the energies up to second-order, we evaluate the coefficients
C3 of the first-order dipolar interactions and the coefficients
C6 and
C8 of the second-order additive and nonadditive interactions. Both the dipolar and dispersion interaction coefficients, for these three-body degenerate systems, show dependences on the geometrical configurations of the three atoms. The nonadditive interactions start to appear in second-order. To demonstrate the results and for applications, the obtained coefficients
Cn are evaluated with highly accurate variationally generated nonrelativistic wave functions in Hylleraas coordinates for $\text{He}(1{\phantom{\rule{0.16em}{0ex}}}^{1}S)\text{\ensuremath{-}}\text{He}(1{\phantom{\rule{0.16em}{0ex}}}^{1}S)\text{\ensuremath{-}}\text{He}(2{\phantom{\rule{0.16em}{0ex}}}^{1}S)$, $\text{He}(1{\phantom{\rule{0.16em}{0ex}}}^{1}S)\text{\ensuremath{-}}\text{He}(1{\phantom{\rule{0.16em}{0ex}}}^{1}S)\text{\ensuremath{-}}\text{He}(2{\phantom{\rule{0.16em}{0ex}}}^{1}P)$, $\text{He}(2{\phantom{\rule{0.16em}{0ex}}}^{1}S)\text{\ensuremath{-}}\text{He}(2{\phantom{\rule{0.16em}{0ex}}}^{1}S)\text{\ensuremath{-}}\text{He}(2{\phantom{\rule{0.16em}{0ex}}}^{1}P)$, and $\text{He}(2{\phantom{\rule{0.16em}{0ex}}}^{3}S)\text{\ensuremath{-}}\text{He}(2{\phantom{\rule{0.16em}{0ex}}}^{3}S)\text{\ensuremath{-}}\text{He}(2{\phantom{\rule{0.16em}{0ex}}}^{3}P)$. The calculations are given for three like nuclei for the cases of hypothetical infinite mass He nuclei, and of real finite mass
4He or
3He nuclei. The special cases of the three atoms in equilateral triangle configurations are explored in detail, and for the cases in which one of the atoms is in a
P state, we also present results for the atoms in an isosceles right triangle configuration or in an equally spaced collinear configuration. The results can be applied to construct potential energy surfaces for three helium atom systems.
Long-range interaction studies of the system ${\mathrm{He}}_{2}(^{3}\ensuremath{\Sigma}^{+})$ based on the multiconfiguration self-consistent-field formalism are reported. In this formalism the long-range contribution to the hyperfine pressure shift of metastable
He(23S) in buffer gas of ground-state He is discussed. It is found by actual computation to be an order of magnitude smaller than that predicted by the many-body perturbation theoretic approach. Possible explanations of the discrepancy are discussed.
The long-range interactions among two- or three-atom systems are of considerable importance in the cold and ultracold research areas for many-body systems. For an ion and an atom, the long-range interaction potential is dominated by the induction (or polarization) potential resulting from the (classical) effect of the ion's electric field on the atom and the leading term of the induction potential is much stronger than the (quantum mechanical) dispersion (or van der Waals) interaction. The present paper focuses on the long-range interaction of the $\mathrm{Li}(2\phantom{\rule{0.16em}{0ex}}^{2}S)\ensuremath{-}\mathrm{Li}(2\phantom{\rule{0.16em}{0ex}}^{2}S)\ensuremath{-}{\mathrm{Li}}^{+}(1\phantom{\rule{0.16em}{0ex}}^{1}S)$ system, to see what changes this induction effect (originating in the electric field of the
Li+ ion) yields in the long-range additive and nonadditive interactions of this three-body system. Using perturbation theory for energies, we evaluate the coefficients
Cn in the potential energy for the three well-separated constituents, where
n refers to the corresponding order in inverse powers of distance, obtaining the additive interaction coefficients
C4,C6,C7,C8,C9 and the nonadditive interaction coefficients
C7,C9. The obtained coefficients
Cn are calculated with highly accurate variationally generated nonrelativistic wave functions in Hylleraas coordinates. Our calculations may be of interest for the study of three-body recombination and for constructing precise potential energy surfaces. We also provide precise evaluations of the long-range potentials for the two-body $\mathrm{Li}(2\phantom{\rule{0.16em}{0ex}}^{2}S)\ensuremath{-}{\mathrm{Li}}^{+}(1\phantom{\rule{0.16em}{0ex}}^{1}S)$ system. For both the two-body and three-body cases, we provide results for the like-nuclei cases of
6Li and
7Li.
For the interactions between a
He(23S) atom and a
He(23P) atom for like isotopes, we report perturbation theoretic calculations using accurate variational wave functions in Hylleraas coordinates of the coefficients determining the potential energies at large internuclear separations. We evaluate the coefficient
C3 of the first order resonant dipole-dipole energy and the van der Waals coefficients
C6,
C8, and
C10 for the second order energies arising from the mutual perturbations of instantaneous electric dipole, quadrupole, and octupole interactions. We also evaluate the leading contribution to the third-order energy. We establish definitive values including treatment of the finite nuclear mass for the $^{3}\mathrm{He}(2\phantom{\rule{0.2em}{0ex}}^{3}S)\text{\ensuremath{-}}^{3}\mathrm{He}(2\phantom{\rule{0.2em}{0ex}}^{3}P)$ and $^{4}\mathrm{He}(2\phantom{\rule{0.2em}{0ex}}^{3}S)\text{\ensuremath{-}}^{4}\mathrm{He}(2\phantom{\rule{0.2em}{0ex}}^{3}P)$ interactions.