The detachment loss dynamics between rubidium atoms (Rb) and oxygen anions (O−) are studied in a hybrid atom–ion trap. The amount of excited rubidium present in the atomic ensemble is actively controlled, providing a tool to tune the electronic quantum state of the system and, thus, the anion–neutral interaction dynamics. For a ground state Rb interacting with O−, the detachment induced loss rate is consistent with zero, while the excited state Rb yields a significantly higher loss rate. The results are interpreted via ab initio potential energy curves and compared to the previously studied Rb–OH− system, where an associative electronic detachment reactive loss process hinders the sympathetic cooling of the anion. This implies that with the loss channels closed for ground-state Rb and O− anion, this system provides a platform to observe sympathetic cooling of an anion with an ultracold heavy buffer gas.
We report close-coupling (CC) quantum dynamics calculations for collisional excitation/de-excitation of the lowest four rotational levels of OD − and of OH − interacting with Rb atoms in a cold ion trap. The calculations are carried out over a range of energies capable of yielding the corresponding rates for state-changing events over a rather broad interval of temperatures which cover those reached in earlier cold trap experiments. They involved sympathetic cooling of the molecular anion through a cloud of laser-cooled Rb atoms, an experiment which is currently being run again through a Heidelberg–Innsbruck collaboration. The significance of isotopic effects is analysed by comparing both systems and the range of temperatures examined in the calculations is extended up to 400 K, starting from a few mK. Both cross sections and rates are found to be markedly larger than in the case of OD − /OH − interacting the He atoms under the same conditions, and the isotopic effects are also seen to be rather significant at the energies examined in the present study. Such findings are discussed in the light of the observed trap losses of molecular anions.
The nonradiative charge-transfer processes in Na
++
87Rb(5
s) collisions have been investigated by using the quantum-mechanical molecular-orbital close-coupling method and the two-center atomic-orbital close-coupling method for the energy range of 10${}^{\ensuremath{-}4}$--5 and 0.3--100 keV/u, respectively. The radiative charge-transfer, radiative-decay, and radiative-association processes have been investigated by using the fully quantum, optical-potential, and semiclassical methods for the energy range of 10${}^{\ensuremath{-}18}$--0.2 eV/u. The nonradiative charge-transfer processes dominate the collisions for energies above 0.2 eV/u and radiative-decay processes dominate in the lower-energy region. At the very low collision energies of 10${}^{\ensuremath{-}18}$--10${}^{\ensuremath{-}3}$ eV/u, the radiative-association process is more important than the radiative charge-transfer process. Most importantly, it is found that the radiative cross sections exhibit Langevin behavior as ${E}^{\ensuremath{-}1/2}$ for energies less than 10${}^{\ensuremath{-}2}$ eV/u.
State-of-the-art ab initio techniques have been applied to compute the potential energy curves of the (BaRb)
+ molecular ion in the Born-Oppenheimer approximation for the singlet and triplet states dissociating into the ground-state
1S Rb
+ ion and the Ba atom in the ground
1S state or the lowest singlet or triplet
d excited states, and for the singlet and triplet states dissociating into the ground-state
2S Rb atom and the ground-state
2S Ba
+ ion. The ground-state potential energy was obtained with the coupled-cluster method restricted to single, double, and nonperturbative triple excitations. The first triplet states in the $\ensuremath{\Sigma}$, $\ensuremath{\Pi}$, and $\ensuremath{\Delta}$ symmetries were computed with the restricted open-shell coupled-cluster method restricted to single, double, and nonperturbative triple excitations. All other excited-state potential energy curves were computed using the equation of motion approach within the coupled-cluster singles, doubles, and linear triples framework. The long-range coefficients describing the electrostatic, induction, and dispersion interactions at large interatomic distances are also reported. The electric transition dipole moments governing the
x ${}^{1}\ensuremath{\Sigma}\ensuremath{\rightarrow}{}^{1}\ensuremath{\Sigma},{}^{1}\ensuremath{\Pi}$ transitions have been obtained as the first residue of the polarization propagator computed with the linear response coupled-cluster method restricted to single and double excitations. Nonadiabatic radial and angular coupling matrix elements as well as the spin-orbit coupling matrix elements have been evaluated using the multireference configuration-interaction method restricted to single and double excitations with a large active space. With these couplings, the spin-orbit-coupled (relativistic) potential energy curves for the 0
+ and 1 states relevant for the running experiments have been obtained. Finally, relativistic transition moments and nonadiabatic coupling matrix elements were obtained from the nonrelativistic results and spin-orbit eigenvectors. The electronic structure input has been employed in the single-channel scattering calculations of the collisional cross sections between the Ba
+ ion and Rb atom. Both nonrelativistic and relativistic potentials were used in these calculations. Our results show that the inelastic cross section corresponding to the charge transfer from the Rb atom to the Ba
+ ion is much smaller than the elastic one over a wide range of energies up to 1 mK. This suggests that sympathetic cooling of the Ba
+ ion by collisions with ultracold Rb atoms should be possible.
Photoassociation resonances in the
87Rb
2 1g state dissociating to
52S+52P1/2 were produced by the excitation of colliding
87Rb atoms in a far-off resonance trap. Levels down to 31 cm${}^{\ensuremath{-}1}$ below the dissociation limit were measured with resonance linewidths of 15 to 20 MHz, and have been located to a one-sigma combined systematic and statistical uncertainty of 50 MHz relative to the
52S+52P1/2 limit. Electron and nuclear spins were fixed to a space-fixed axis by circularly polarized optical pumping, so that only states with total nuclear spin
I=3 were excited, thereby greatly simplifying the spectrum. The analysis of the data yielded hyperfine coupling parameters
A(v), vibrational
G(v), and rotational
B(v) parameters. The
G(v) parameters could be fit to an rms accuracy of about 0.01 cm${}^{\ensuremath{-}1}$ to a potential constructed from current
C3 and
C6 long-range dispersion parameters plus an ab initio potential that was adjusted in depth and with quadratic terms in the internuclear distance added to the inner wall.
By employing ab initio computed intermolecular potential energy surfaces we calculate the radiative association probabilities and rates for two different associative mechanisms involving trapped molecular ions N2+(2Σg) interacting either directly with ultracold Rb atoms or undergoing charge-exchange (CE) processes leading to the formation of complexes of the strongly exothermic products N2(X1Σg) plus Rb+(1S0). The two processes are expected to provide possible paths to ion losses in the trap within the timescale of experiments. The present calculations suggest that the associative rates for the 'vibrational' direct process are too small to be of any significant importance at the millikelvin temperatures considered in the experiments, while the 'vibronic' path into radiatively associating the CE products has a probability of occurring which is several orders of magnitude larger. However the reaction rate constants attributed to non-adiabatic CE [F. H. J. Hall and S. Willist, Phys. Rev. Lett., 2012, 109, 233202] are in turn several orders of magnitude larger than the radiative ones calculated here, thereby making the primary experimental process substantially unaffected by the radiative losses channel.