Ionization potentials of halides. Substituent effects in Cl-, Br-, and I-centered radical cations

The first vertical ionization potentials (I) of halides HalX (Hal = Cl, Br, I; X is an inorganic or organic substituent) are linearly related to the inductive (σI), resonance (σR+), and polarizability (σα) constants of the substituents X (I = a + bσI + cσR+ + dσα). As the atomic number of the Hal element in the Hal·+X radical cations increases, the inductive interaction is strengthened while the polarizability interaction is weakened. Conjugation remains virtually independent of the Hal atom. The resonance σR+-constants of the MX3 (M = Si, Ge, Sn, Pb) substituents bound to the Hal·+ radical cation centers were first calculated.