Photoelectron Velocity Map Imaging Spectroscopy of the Beryllium Sulfide Anion, BeS

Slow electron velocity map imaging (SEVI) spectroscopy was used to examine the BeS^- anion to neutral ground-state transition, X ²Σ⁺ → X ¹Σ⁺. Rotational constants, vibrational intervals, and the electron binding energy of BeS^- were determined. Partially resolved rotational contours were seen due to the relatively small moment of inertia of beryllium sulfide. Upon analysis of the rotational contours, it was found that changes in the molecular rotational angular momentum, ΔN = -1, -2, -3, and -4, facilitated photodetachment at near-threshold photon energies. The electron affinity of BeS was found to be 2.3346(2) eV. SEVI spectra recorded using photon energies near the threshold for Δv = -1 processes exhibited features that were associated with a dipole-bound state (DBS) of BeS^-. Autodetachment spectroscopy was used to probe this state, and rotationally resolved data were obtained for the DBS ²Σ⁺, v' = 0 - X ²Σ⁺, v″ = 0 transition. Analysis of this structure provided the rotational constants for BeS^- X, v″ = 0, and the electron binding energy of the DBS. Electronic structure calculations, performed at the RCCSD(T) and MRCI levels of theory, gave predictions that were in good agreement with the experimental observations.