Abstract

The dynamics of Rydberg states in condensed matter is still a field to be unravelled. The radius of low-n Rydberg states is comparable to the nearest neighbour distance in rare gas solids. Consequently, following photoexcitation of such states in a solid matrix, there will be a short-range repulsive interaction between the Rydberg electron and the electronic cloud of the neighbouring matrix atoms. This repulsion leads to a local expansion around the electronically excited center and results in the formation of a "microscopic cavity", or "bubble", surrounding the molecule as the solvent atoms are pushed asunder to a new equilibrium position /1-4/. In conventional spectroscopy, this is inferred from the large blue gas-to-matrix shifts of absorption bands and the strong absorption-emission Stokes shifts.

© 1996 Optical Society of America