Optical Control of Reactions between Water and Laser-Cooled Be⁺ Ions

Abstract

We investigate reactions between laser-cooled Be⁺ ions and room-temperature water molecules using an integrated ion trap and high-resolution time-of-flight mass spectrometer. This system allows simultaneous measurement of individual reaction rates that are resolved by reaction product. The rate coefficient of the Be⁺(²S_1/2) + H₂O → BeOH⁺ + H reaction is measured for the first time and is found to be approximately two times smaller than predicted by an ion-dipole capture model. Zero-point-corrected quasi-classical trajectory calculations on a highly accurate potential energy surface for the ground electronic state reveal that the reaction is capture-dominated, but a submerged barrier in the product channel lowers the reactivity. Furthermore, laser excitation of the ions from the ²S_1/2 ground state to the ²P_3/2 state opens new reaction channels, and we report the rate and branching ratio of the Be⁺(²P_3/2) + H₂O → BeOH⁺ + H and H₂O⁺ + Be reactions. The excited-state reactions are nonadiabatic in nature.