Time-resolved relaxation dynamics of Hgn

Electron-nuclear relaxation dynamics are studied in Hgn 2 (11<n<16,n518) using time-resolved photoelectron imaging. The excess electron in the anion uniquely occupies the p band and is excited intraband by 1.53 eV pump photons; the subsequent dynamics are monitored by photodetachment at 3.06 eV and measurement of the photoelectron images as a function of pump-probe delay. The initially excited state decays on a time scale of ;10 ps, and subsequent relaxation dynamics reveal a smooth evolution of the photoelectron spectra towards lower electron kinetic energy over 50–100 ps. Qualitatively, the relaxation process is captured by a simple kinetic model assuming a series of radiationless transitions within a dense manifold of electronic states. All the clusters studied show similar dynamics with the exception of Hg11 2 in which the initially prepared state does not decay as quickly as the others. © 2004 American Institute of Physics. @DOI: 10.1063/1.1809573#