Accurate ab initio calculations of RaF electronic structure appeal to more laser-spectroscopical measurements

Recently, a breakthrough has been achieved in laser-spectroscopic studies of short-lived radioactive compounds with the first measurements of the radium monofluoride molecule (RaF) UV/vis spectra. We report results from high-accuracy ab initio calculations of the RaF electronic structure for ground and low-lying excited electronic states. Two different methods agree excellently with experimental excitation energies from the electronic ground state to the ²Π_1/2 and ²Π_3/2 states, but lead consistently and unambiguously to deviations from experimental-based adiabatic transition energy estimates for the ²Σ_1/2 excited electronic state, and show that more measurements are needed to clarify spectroscopic assignment of the ²Δ state.