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Optical spectroscopy of atoms and molecules is a field where one usuallyoperates very far from thermal equilibrium conditions. A prominent example isspectroscopy of thin vapors, where the pump irradiation leads to a nonequilibrium distribution within the electronic structure that is well shieldedfrom the environment. Here we describe experimental work investigatingabsorption and emission lines of rubidium vapor subject to a noble buffer gasenvironment with pressure 100 to 200 bar, a regime interpolating between usualgas phase and liquid solid state conditions. Frequent elastic collisions in thedense buffer gas sample cause a large coupling to the environment. We give adetailed account of recent observations of the Kennard Stepanov scaling, aBoltzmann like thermodynamic frequency scaling between absorption and emissionprofiles, for both atomic and molecular rubidium species in the gaseousenvironment. Our observations are interpreted as due to the thermalization ofalkali noble gas submanifolds in both ground and electronically excited statesrespectively. Both pressure broadening and shift of the high pressure buffergas D lines system are determined. We also discuss some prospects, includingpossible advances in collisional laser cooling and optical thermometry.

Rubidium spectroscopy at high-pressure buffer gas conditions: detailed balance in the optical interaction of an absorber coupled to a reservoir