Vibrational relaxation and dephasing of Rb2 attached to helium nanodroplets

Abstract

The vibrational wave-packet dynamics of diatomic rubidium molecules (Rb₂) 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 1³Σ⁺_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.