Dynamics of electrons in ammonia cages: The discovery system of solvation

Two centuries ago solvated electrons were discovered in liquid ammonia and a century later the concept of the solvent cage was introduced. Here, we report a real time study of the dynamics of size-selected clusters, n=20 to 60, of electrons in ammonia, and, for comparison, that of electrons in water cages. Unlike the water case, the observed dynamics for ammonia indicates the formation, through a 100 fs temperature jump, of a solvent collective motion in a 500 fs relaxation process. The agreement of the experimental results - obtained for a well-defined n, gated electron kinetic energy, and time delay - with molecular dynamics theory suggests the critical and different role of the kinetic energy and the librational motions involved in solvation.