Charge carrier dynamics in semiconducting mercury cluster anions

We have examined size-dependent electronic relaxation dynamics in isolated semiconducting mercury cluster anions using time-resolved photoelectron imaging. Relaxation following excitation from within the conduction (p-) band occurs on an 3‐40ps timescale and is attributed to non-adiabatic relaxation through the p-band. Exciting an electron from the valence (s-) band into the conduction band creates an electron‐hole pair that relaxes prior to Auger emission. The dynamics associated with this feature occur on an 500fs timescale and are attributed to either a hole-induced contraction of the cluster or electron‐electron scattering.