According to Quantum Mechanics (and a few degrees of approximation), we find something called Koopman's theorem. It states that "ionization energies of a molecule are equal to the eigenvalues of the Fock operator associated to the occupied molecular orbitals" (
WikiPedia, "Koopman's Theorem").
This method is kinda complicated, and makes a lot of approximations...if you don't have a background in quantum mechanics, I don't think it's worth getting into
. You have to know the wavefunctions for the electrons, and Slater determinants, a whole slew of stuff.
It's best just to get the data by experimenting. Or looking it up somewhere...