\textit{Ab initio} study of reactive collisions between Rb(${}^{2}S$) or Rb(${}^{2}P$) and OH${}^{-}$(${}^1{\Sigma }^{+}$)

Abstract

A theoretical rate constant for the associative detachment reaction Rb(${}^{2}S$)$+$OH${}^{-}$(${}^1{\Sigma }^{+}$)$\to$ RbOH(${}^1{\Sigma }^{+}$)$+e^{-}$ of 4$\times$10${}^{-10}$cm${}^3$s${}^{-1}$ at 300 K has been calculated. This result agrees with the experimental rate constant of 2${}_{-1}^{+2}\times 10^{-10}$cm${}^3$s${}^{-1}$ obtained by Deiglmayr \textit{et al.} (Phys. Rev. A 86, 2012) for a temperature between 200 K and 600 K. A Langevin-based dynamics which depends on the crossing point between the anion (RbOH${}^{-}$) and neutral (RbOH) potential energy surfaces has been used. The calculation were performed using the ECP28MDF effective core potential to describe the rubidium atom at the CCSD(T) level of theory and extended basis sets. The effect of ECPs and basis set on the height of the crossing point, and hence the rate constant, has been investigated. The temperature dependence of the latter is also discussed. Preliminary work on the potential energy surface for the excited reaction channel Rb(${}^{2}P$)+OH${}^{-}$(${}^1{\Sigma }^{+}$) calculated at the CASSF-icMRCI level of theory is shown. We qualitatively discuss the charge transfer and associative detachment reactions arising from this excited entrance channel.

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Cited by in corpus (5)

• Cold hybrid ion-atom systems
• Associative detachment in anion-atom reactions involving a dipole-bound electron
• Cold reactive and non-reactive collisions of Li and Rb with C${}_2^{-}$: implications for hybrid trap experiments
• Cold collisions of C${}_2^{-}$ anions with Li and Rb atoms in hybrid traps
• Reactivity of hydrated hydroxide anion cluster OH(H${}_2$O)${}_n^{-}$ with H and Rb: an ab initio study