  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 \emph{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 $^2\Pi_{1/2}$ and $^2\Pi_{3/2}$ states, but lead consistently and
unambiguously to deviations from experimental-based adiabatic transition energy
estimates for the $^2\Sigma_{1/2}$ excited electronic state and show that more
measurements are needed to clarify spectroscopic assignment of the $^2\Delta$
states.
