Femtosecond dynamics of cage relaxation following NO Rydberg states excitation in condensed matter

Summary form only given. The dynamics of Rydberg states in condensed matter is still a field to be unraveled. As far as low-n Rydberg states in solids are concerned, the radius of the orbital is of the same order of magnitude as the nearest neighbor distance and it is observed that their absorption bands are strongly blue shifted as compared with the gas phase energies. This repulsion leads to formation of a "bubble" or "microcavity" around the excited atom or molecule, as the solvent atoms are pushed asunder to a new equilibrium position. We have probed this "bubble" formation in real time using the fluorescence depletion technique. 250-fs pulses at 195.8 and 187 nm were used to pump the Rydberg A/sup 2//spl Sigma//sup +//3s/spl sigma/(v=0) level of NO in Ar matrices with the probe wave-length set at the 3s/spl sigma/-4s/spl sigma/ transition as determined from preliminary nanosecond experiments. The A(v=0) fluorescence signal was recorded as a function of pump-probe delay.