Study of the ArBr−, ArI−, and KrI− anions and the corresponding neutral van der Waals complexes by anion zero electron kinetic energy spectroscopy

Abstract

Three rare gas halide (RgX⁻) anions, ArBr⁻, ArI⁻, and KrI⁻, and the corresponding open‐shell van der Waals complexes, ArBr, ArI, and KrI, were studied with anion zero electron kinetic energy (ZEKE) spectroscopy. Photodetachment of each anion accesses the three lowest‐lying electronic states (the X1/2, I3/2, and II1/2 states) of the neutral complex. The spectra for each system reveal well‐resolved progressions in the low frequency vibrations of the anion and the three neutral electronic states, providing a detailed spectroscopic probe of the Rg⋅X⁻ and Rg⋅X interaction potentials. The line shapes observed in the ZEKE spectra are analyzed in terms of the line strengths of the underlying rotational transitions. From our data, we construct the potential energy curve for each neutral state as well as for the anion, and these interaction potentials are compared to potentials obtained from scattering and ion mobility experiments.