Extracting double minima excited state potentials from bound-continuum spectroscopic data

► We present a systematic procedure to generate Born-Oppenheimer potential surfaces from bound-continuum transition data. ► Our method is able to address cases involving multiple minima and calculate values above the dissociation energy. ► We construct a double well potential of Na2 to high accuracy with no prior knowledge of its structure. ► The procedure can simultaneously calculate dipole moment surfaces and is also applicable to polyatomic molecules.