The one-dimensional configuration coordinate model (1D-CCM) is widely used for the analysis of photoluminescence in molecules and doped solids, and relies on a linear combination of the equilibrium nuclear configurations of ground and excited states. It delivers an estimation of the energy barrier at which ground and excited state curves cross, semiclassically linked to nonradiative transition rate and thermal quenching. To assess its predictive power for the latter properties, we propose a new optimized configuration path (OCP) method in which the ground-state and excited-state forces are mixed instead of their configurations. We also define another one-parameter model thanks to a double energy parabola hypothesis (DEPH). We compare the OCP method and the DEPH reference with the 1D-CCM for three paradigmatic 4 f -5 d phosphors Y3Al5O12 :Ce, Lu2SiO5 :Ce, and YAlO3:Ce. We find that the OCP and DEPH methods yield similar results with geometries that have significantly lower ground-state energies than the 1D-CCM for the same 4 f -5 d energy difference. However, the OCP method suffers from the appearance of multiple local minima, rendering the clear determination of the optimal geometry very difficult in practice. Still the OCP method allows one to quantify the deviations from the 1D-CCM, therefore increasing confidence in the lower bound obtained from the DEPH for the 4 f -5 d crossing barrier, and its comparison with the energy of the autoionization thermal quenching mechanism. We expect the OCP approach to be applicable to other luminescent materials or molecules.