Vibrational relaxation and dephasing of Rb2 attached to helium nanodroplets.

The vibrational wave-packet dynamics of diatomic rubidium molecules (Rb(2)) in triplet states formed on the surface of superfluid helium nanodroplets is investigated both experimentally and theoretically. Detailed comparison of experimental femtosecond pump-probe spectra with dissipative quantum dynamics simulations reveals that vibrational relaxation is the main source of dephasing. The rate constant for vibrational relaxation in the first excited triplet state 1(3)Σ(g)+ is found to be constant γ ≈ 0.5 ns(-1) for the lowest vibrational levels v ≲ 15 and to increase sharply when exciting to higher energies.