Alkali atoms attached to vortex-hosting helium nanodroplets.

Light absorption or fluorescence excitation spectroscopy of alkali atoms attached to 4He droplets is investigated as a possible way for detecting the presence of vortices. To this end, we have calculated the equilibrium configuration and energetics of alkali atoms attached to a 4He1000 droplet hosting a vortex line using 4He density functional theory. We use them to study how the dipole absorption spectrum of the alkali atom is modified when the impurity is attached to a vortex line. Spectra are found to be blue-shifted (higher frequencies) and broadened compared to vortex-free droplets because the dimple in which the alkali atom sits at the intersection of the vortex line and the droplet surface is deeper. This effect is smaller for lighter alkali atoms and all the more so when using a quantum description since, in this case, they sit further away from the droplet surface on average due to their zero-point motion. Spectral modifications due to the presence of a vortex line are minor for np ← ns excitation and therefore insufficient for vortex detection. In the case of higher n'p ← ns or n's ← ns (n' > n) excitations, the shifts are larger as the excited state orbital is more extended and therefore more sensitive to changes in the surrounding helium density.

Dynamics of impurity clustering in superfluid 4He nanodroplets.

The capture of multiple impurities by 4He droplets is investigated using real time dynamics within the density functional approach applied to liquid helium. We study the case of two or six Ar atoms colliding with a 4He5000 droplet either in its ground state or hosting a six-vortex array. Depending on initial kinematic conditions, two different Ar structures are found: either a compact, gas-phase like cluster, or a loosely bound metastable cluster with helium density caged inside. In the presence of the vortex array, the argon atoms are deflected by the superfluid flow, tending to orbit around the vortex cores. The Ar atoms end up being trapped together in a loosely bound structure attached to the central vortex core.

4s to 5s and 4p photoexcitation dynamics of K atoms from the surface of helium nanodroplets: a theoretical study.

We study the photodissociation of the potassium atom from a superfluid helium nanodroplet upon 5s 2S or 4p 2P excitation using the time-dependent helium density functional method (He-TDDFT). The importance of quantum effects is assessed by comparing the absorption spectrum obtained for a classical or a quantum description of the K atom. In the case of the 5s 2S ← 4s 2S excitation the difference is rather large, and we use a quantum description for the ensuing direct dissociation dynamics. In the case of the 4p 2P ← 4s 2S absorption spectrum, the difference is much smaller, hence a classical description of K is used to describe 4p 2P excitation dynamics. Excitation to the 4p 2Σ1/2 state leads to the direct dissociation of the K atom, while the 4p 2Π3/2 state initially leads to the formation of an exciplex and the 4p 2Π1/2 state to a bouncing atom above the droplet surface. Remarkably, electronic relaxation can be observed for the latter two states, leading to spin-orbit relaxation and the binding of the initially departing one-atom excimer as a ring excimer for the 2P3/2 state and to the formation of a bound, ring excimer for the 2Π1/2 state.

Desorption dynamics of RbHe exciplexes off He nanodroplets induced by spin-relaxation.

Doped He nanodroplets are ideal model systems to study the dynamics of elementary photophysical processes in heterogeneous nanosystems. Here we present a combined experimental and theoretical investigation of the formation of free RbHe exciplex molecules from laser-excited Rb-doped He nanodroplets. Upon excitation of a droplet-bound Rb atom to the 5p3/22Π3/2-state, a stable RbHe exciplex forms within about 20 ps. Only due to 2Π3/2 → 2Π1/2 spin-relaxation does the RbHe exciplex detach from the He droplet surface with a half life of about 700 ps, given by the spin-relaxation time and the coupling of spin and translational degrees of freedom.

Capture of Xe and Ar atoms by quantized vortices in 4He nanodroplets.

We present a computational study, based on time-dependent Density Functional theory, of the real-time interaction and trapping of Ar and Xe atoms in superfluid 4He nanodroplets either pure or hosting quantized vortex lines. We investigate the phase-space trajectories of the impurities for different initial conditions and describe in detail the complex dynamics of the droplets during the capture of the impurities. We show that the interaction of the incoming atom with the vortex core induces large bending and twisting excitations of the vortex core lines, including the generation of helical Kelvin waves propagating along the vortex core. We have also calculated the stationary configurations of a 4He droplet hosting a 6-vortex array whose cores are filled with Ar atoms. As observed in recent experiments, we find that doping adds substantial rigidity to the system, such that the doped vortex array remains stable, even at low values of the angular velocities where the undoped vortices would otherwise be pushed towards the droplet surface and be expelled.

Imaging Excited-State Dynamics of Doped He Nanodroplets in Real-Time.

The real-time dynamics of excited alkali metal atoms (Rb) attached to quantum fluid He nanodroplets is investigated using femtosecond imaging spectroscopy and time-dependent density functional theory. We disentangle the competing dynamics of desorption of excited Rb atoms off the He droplet surface and solvation inside the droplet interior as the Rb atom is ionized. For Rb excited to the 5p and 6p states, desorption occurs on starkly differing time scales (∼100 versus ∼1 ps, respectively). The comparison between theory and experiment indicates that desorption proceeds either impulsively (6p) or in a transition regime between impulsive dissociation and complex desorption (5p).