Long-range interactions of hydrogen atoms in excited states. I. 2S-1S interactions and Dirac-δ perturbations

The theory of the long-range interaction of metastable excited atomic states with ground-state atoms is analyzed. We show that the long-range interaction is essentially modified when quasi-degenerate states are available for virtual transitions. A discrepancy in the literature regarding the van der Waals coefficient C_6(2S;1S) describing the interaction of metastable atomic hydrogen (2S state) with a ground-state hydrogen atom is resolved. In the the van der Waals range a_0 > hbar c/L, we find an oscillatory tail with a negligible interaction energy below 10^(-36) Hz. Dirac-delta perturbations to the interaction are also evaluated and results are given for all asymptotic distance ranges; these effects describe the hyperfine modification of the interaction, or, expressed differently, the shift of the hydrogen 2S hyperfine frequency due to interactions with neighboring 1S atoms. The 2S hyperfine frequency has recently been measured very accurately in atomic beam experiments.