Optical spectroscopy of atoms and molecules is a field where one usually operates very far from thermal equilibrium conditions. A prominent example is spectroscopy of thin vapors, where the pump irradiation leads to a non-equilibrium distribution within the electronic structure that is well shielded from the environment. Here we describe experimental work investigating absorption and emission lines of rubidium vapor subject to a noble buffer gas environment with pressure 100 -200 bar, a regime interpolating between usual gas phase and liquid/solid state conditions. Frequent elastic collisions in the dense buffer gas sample cause a large coupling to the environment. We give a detailed account of recent observations of the Kennard-Stepanov scaling, a Boltzmann-like thermodynamic frequency scaling between absorption and emission profiles, for both atomic and molecular rubidium species in the gaseous environment. Our observations are interpreted as due to the thermalization of alkali-noble gas submanifolds in both ground and electronically excited states respectively. Both pressure broadening and shift of the high pressure buffer gas D-lines system are determined. We also discuss some prospects, including possible advances in collisional laser cooling and optical thermometry.

We study laser cooling of atomic gases by collisional redistribution of fluorescence. In a high pressure buffer gas regime, frequent collisions perturb the energy levels of alkali atoms, which allows for the absorption of a far red detuned irradiated laser beam. Subsequent spontaneous decay occurs close to the unperturbed resonance frequency, leading to a cooling of the dense gas mixture by redistribution of fluorescence. Thermal deflection spectroscopy indicates large relative temperature changes down to and even below room temperature starting from an initial cell temperature near 700 K. We are currently performing a detailed analysis of the temperature distribution in the cell. As we expect this cooling technique to work also for molecular-noble gas mixtures, we also present initial spectroscopic experiments on alkali-dimers in a dense buffer gas surrounding.