Authors: Gianturco, F. A.; Dorfler, A. D.; Willitsch, S.; Yurtsever, E.; Gonzalez-Lezana, T.; Villarreal, P.
Journal: PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Publication date: 2019/04/28
Abstract: 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 N-2(+)((2)sigma(g)) interacting either directly with ultracold Rb atoms or undergoing charge-exchange (CE) processes leading to the formation of complexes of the strongly exothermic products N-2(X-1 sigma(g)) plus Rb+(S-1(0)). 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.