Nonlinear pressure shifts of alkali-metal atoms in inert gases

Precise measurements show that the microwave resonance frequencies of ground-state Rb or Cs atoms have a nonlinear dependence on the pressure of the buffer gases Ar and Kr. No nonlinearities were observed in the gases He or N(2). These observations strongly suggest that the nonlinearities are due to the van der Waals molecules that form in Ar and Kr, but not in He or N(2). The nonlinear part of the shifts is largest in the pressure range of a few tens of torr, similar to the operating pressures of gas-cell atomic clocks. The observed shifts are very well described by a simple function, parametrized by the effective three-body formation rate of molecules and by the effective product of the collisionally limited lifetime times the shift of the hyperfine coupling coefficient in the molecule.