Rubidium dimers residing on the surface of He nanodroplets are doubly ionized by an intense femtosecond laser pulse leading to fragmentation into a pair of
Rb+ ions. We show that the kinetic energy of the
Rb+ fragment ions can be used to identify dimers formed in either the
X $^{1}{\mathrm{\ensuremath{\Sigma}}}_{g}^{+}$ ground state or in the lowest-lying triplet state, $a\text{ }^{3}{\mathrm{\ensuremath{\Sigma}}}_{u}^{+}$. From the experiment, we estimate the abundance ratio of dimers in the
a and
X states as a function of the mean droplet size and find values between $4\ensuremath{\mathbin:}1$ and $5\ensuremath{\mathbin:}1$. Our technique applies generally to dimers and trimers of alkali atoms, here also demonstrated for
Li2,
Na2, and
K2, and will enable femtosecond time-resolved measurements of their rotational and vibrational dynamics, possibly with atomic structural resolution.
Silver atoms, initially embedded in nanodroplets of superfluid helium (roughly
104 atoms in size), are found to move to the surface and desorb when excited to the broadened
5p level. The absorption of a second photon within less than 10 ns leads to the population of previously unobserved Rydberg states
(20<n<60) of free silver atoms. This is the first result showing laser induced movement of a foreign atom from the inside to the surface of a nanodroplet of superfluid helium.
Spectroscopy of doped helium nanodroplets has become, in recent years, a popular tool for the study of bothfinite size samples of the helium quantum fluid and molecules isolated in this sub Kelvin environment. Whilemany dopants migrate to the center of the droplet, alkali (Ak) atoms in their ground electronic state, becauseof their so weak interaction with He, remain at the surface, the latter being in this way slightly distortedexhibiting a dimple. However, when in their first excited states, Ak atoms are forming exciplexes. These areanisotropic with the central atom surrounded by a ring of He atoms located in the nodal plane of the valenceelectron pz orbital. Structural properties, obtained by DMC and PIMC, are presented here for some Ak -Hen exciplexes.Ak2 dimers in helium environment have also gained interest in this last decade, in connexion with the generationof ultracold molecules. When attached to helium droplets, Ak atoms can float on the surface andform molecules in cold collisions. DMC and PIMC methods are used to compute energetics and structuralinformations for Rb2 in helium. In particular, the orientation of the dimer relative to the droplet surface isexamined.
Helium dimer in its metastable triplet electronic state, He
2(a 3Σu+), is a promising candidate for direct laser cooling and precision measurements. Interactions and collisions involving He
2(a 3Σu+) remain unexplored in ultracold and cold energy domains. Here, we present the first theoretical investigation of intermolecular interactions and collision dynamics of He
2(a 3Σu+)+Ne van der Waals complex. For the ground electronic state,
X 3A′, we employ a spin-restricted coupled cluster method with single, double, and noniterative triple excitations. The resulting interaction potential exhibits an extremely shallow well with a depth of 4.612 cm
−1. We construct a three-dimensional vibrationally averaged potential energy surface. Using this surface, we perform full close-coupling calculations including fine-structure levels of He
2(a 3Σu+) to investigate collisional excitation and quenching induced by Ne. We analyze the low-energy scattering dynamics and model resonant features associated with quasi-bound states supported by interaction potential. Propensity rule for fine-structure conserving transitions is established. We additionally consider He
2+Ar collisions and compare their energy dependence and resonance structure with those of He
2+Ne. The He
2+Ar system exhibits a richer resonance structure, highlighting the sensitivity of low-energy scattering to interaction potential and reduced mass. Calculated PES and scattering properties provide a reliable benchmark for description of He
2+Ne van der Waals complex and may be useful for interpretation of future experimental spectra and collision measurements.
We have performed three theoretical simulations relevant for describing collisions among laser-cooled silver atoms and for the formation of Ag 2 molecules from these colliding atoms. Firstly, we determined the relativistic electronic structure of Ag 2 molecules in ground and low-lying excited states. Secondly, we computed rotational and vibrational levels of the ground and excited electronic states as well as rovibrationally averaged electric transition dipole moments. Using this knowledge, we analyzed a simplified quantum-mechanical model of the one-photon photoassociation process to form electronically excited Ag 2 from microkelvin Ag atoms and make predictions for lineshapes and saturation effects as functions of laser frequency and intensity. Finally and thirdly, we performed coupled-channels calculations, numerical solutions of sets of coupled radial Schrödinger equations of ultracold ground-state Ag collisions in an external magnetic field. These calculations include the effects of two Born-Oppenheimer potentials as well as hyperfine Fermi-contact and Zeeman interactions. We discuss the expected range of s -wave scattering lengths as well as strengths and distribution of Fano-Feshbach resonances as a function of the magnetic-field strength for the Ag 107 and Ag 109 isotopes. We highlight the periodicity of the scattering length with small changes in the depths of the Born-Oppenheimer potentials. The Fano-Feshbach resonances can be used to magneto-associate ultracold Ag atoms into weakly bound ground-state Ag 2 dimers.