Dynamics of He2∗ triplet state excimer bubbles in superfluid 4He

Time-dependent density functional theory calculations for bulk superfluid 4He were carried out to model dynamics around He2∗ excimers after optical excitation from the 3a to 3d state. The liquid dynamics occurring after a sudden change in the helium-liquid interaction results in interfacial dynamics, which can be divided into three different modes: (1) non-linear processes yielding shock and solitonic progressions, (2) fast interfacial dynamics related to thinning of the liquid-gas interface that occurs within few picoseonds and (3) slow spherical breathing motion of the liquid-gas interface with recursion times up to 110 ps. The long-range repulsive tail (R > 12 Å) in the He-He2∗ interaction is found to play an important role in determining the recursion time of the solvent cavity breathing mode. As energy differences of just few wavenumbers in this region are sufficient to produce large changes in the recursion time, none of the pair potentials derived from the first principles could reproduce the experimental data [V.A. Benderskii, J. Eloranta, R. Zadoyan, V.A. Apkarian, J. Chem. Phys. 117 (2002) 1201]. Therefore it is concluded that the pump-probe experiments measure energy differences that are not possible to calculate using the current electronic structure methods. The results obtained from the density functional theory calculations are consistent with the proposed experimental scheme.