[en] The principle of microscopic time-reversal of physical processes, detailed balance, is widely used and depended upon in the theoretical community as a connection between the inverse processes of photorecombination (PR) and photoionization (PI). This paper reports on a novel use of detailed balance and the comparison of experimental results obtained by two very distinct techniques to determine both the metastable fraction of an ion beam and partial Sc³⁺ PR cross sections and partial Sc²⁺ PI cross sections for the ground state and for two metastable states. The Sc²⁺ to Sc³⁺ system presents a unique opportunity to obtain comprehensive state-selective information by combining results from PR and PI experiments