Dynamics of photo-excited Cs atoms attached to helium nanodroplets

TL;DR

This study investigates the ultrafast dynamics of photo-excited cesium atoms on helium nanodroplets, revealing different desorption mechanisms and spin-orbit relaxation processes through femtosecond spectroscopy and theoretical comparisons.

Contribution

It provides the first experimental measurements of desorption and exciplex formation timescales for Cs atoms on helium nanodroplets, and compares these with theoretical models.

Findings

Desorption occurs only when excitation is blue-shifted from resonance.

Different desorption mechanisms are identified for different excited states.

Results agree with previous density-functional theory simulations.

Abstract

We present an experimental study of the dynamics following the photo-excitation and subsequent photo-ionization of single Cs atoms on the surface of helium nanodroplets. The dynamics of excited-Cs-atom desorption and re-adsorption as well as CsHe exciplex formation are measured using femtosecond pump-probe velocity-map-imaging spectroscopy and ion-time-of-flight spectrometry. The timescales for the desorption of excited Cs atoms off helium nanodroplets as well as the timescales for CsHe exciplex formation are experimentally determined for the 6p states of Cs. For the 6p $^2\Pi_ {1/2}$ state, our results confirm that the excited Cs atoms only desorb from the nanodroplet when the excitation wavenumber is blue-shifted from the $6p\,^2\Pi_ {1/2} \leftarrow 6s\,^2\Sigma_ {1/2}$ resonance. Our results suggest that the dynamics following excitation to the 6p $^2\Pi_ {3/2}$ state can be described by an evaporation-like desorption mechanism, whereas the dynamics arising from excitation to the 6p $^2\Sigma_ {1/2}$ state is indicative for a more impulsive desorption process. Furthermore, our results suggest a helium-induced spin-orbit relaxation from the the 6p $^2\Sigma_ {1/2}$ state to the 6p $^2\Pi_ {1/2}$ state. Our findings largely agree with the results of time-dependent $^4$He-density-functional theory (DFT) simulations published earlier [Coppens et al., Eur. Phys. J. D 73, 94 (2019)].