Andreas Kautsch

Electronic Relaxation after Resonant Laser Excitation of Cr in Superfluid Helium Nanodroplets

Chromium (Cr) atoms embedded into helium nanodroplets (HeN) are ejected from the droplets upon photoexcitation. During ejection they undergo electronic relaxation resulting in bare Cr atoms in various excited states. In a study of the relaxation process we present absorption spectra observed via laser induced fluorescence and beam depletion as well as dispersed fluorescence spectra and time-resolved fluorescence measurements. Broad and shifted absorption structures were found for the strong z7P° ← a7S3 and y7P° ← a7S3 excitations from the ground state. Emission lines are, in contrast, very narrow, which indicates that fluorescence is obtained from bare excited Cr atoms after ejection. Upon excitation into the y7P2,3,4° states we observed fluorescence from y7P2°, z5P1,2,3°, and z7P2,3,4°, indicating that these states are populated by electronic relaxation during the ejection processes. Relative population ratios are obtained from the intensities of individual spectral lines. Excitation into the z7P2,3,4° states resulted in fluorescence only from z7P2°. Estimates of the time duration of the ejection process are obtained from time-resolved measurements.

One- and Two-Color Resonant Photoionization Spectroscopy of Chromium-Doped Helium Nanodroplets

We investigate the photoinduced relaxation dynamics of Cr atoms embedded into superfluid helium nanodroplets. One- and two-color resonant two-photon ionization (1CR2PI and 2CR2PI, respectively) are applied to study the two strong ground state transitions z7P2,3,4° ← a7S3 and y7P2,3,4° ← a7S3. Upon photoexcitation, Cr* atoms are ejected from the droplet in various excited states, as well as paired with helium atoms as Cr*–Hen exciplexes. For the y7P2,3,4° intermediate state, comparison of the two methods reveals that energetically lower states than previously identified are also populated. With 1CR2PI we find that the population of ejected z5P3° states is reduced for increasing droplet size, indicating that population is transferred preferentially to lower states during longer interaction with the droplet. In the 2CR2PI spectra we find evidence for generation of bare Cr atoms in their septet ground state (a7S3) and metastable quintet state (a5S2), which we attribute to a photoinduced fast excitation–relaxation cycle mediated by the droplet. A fraction of Cr atoms in these ground and metastable states is attached to helium atoms, as indicated by blue wings next to bare atom spectral lines. These relaxation channels provide new insight into the interaction of excited transition metal atoms with helium nanodroplets.

Electronic Relaxation Processes Of Transition Metal Atoms In Helium Nanodroplets

Spectroscopy of doped superfluid helium nanodroplets (HeN ) gives information about the influence of this cold, chemically inert, and least interacting matrix environment on the excitation and relaxation dynamics of dopant atoms and molecules a. We present the results from laser induced fluorescence (LIF), photoionization (PI), and mass spectroscopy of Cr b and Cu c doped HeN . From these results, we can draw a comprehensive picture of the complex behavior of such transition metal atoms in HeN upon photo-excitation. The strong Cr and Cu ground state transitions show an excitation blueshift and broadening with respect to the bare atom transitions which can be taken as indication for the solvation inside the droplet. From the originally excited states the atoms relax to energetically lower states and are ejected from the HeN . The relaxation processes include bare atom spin-forbidden transitions, which clearly bears the signature of the HeN influence. Two-color resonant two-photon ionization (2CR2PI) also shows the formation of bare atoms and small Cr-Hen and Cu-Hen clusters in their ground and metastable states c d. Currently, Cr dimer excitation studies are in progress and a brief outlook on the available results will be given.