Excitation of Rydberg states in isolated C-60 is studied by time-resolved photoelectron spectroscopy in a femtosecond two-color pump-probe experiment. The relaxation time for electron-electron interaction is determined to be approximately 100 fs with the t(1g)(LUMO+1) orbital being considered to define the doorway state in a nonadiabatic multielectron excitation process. The internal energy stored in vibrational modes of the C-60 at 770 K is found to support the excitation process very efficiently while in cold C-60 (80 K), no significant Rydberg population is detected.
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