Vertical ionization energies of halogen anions in solution

Abstract

Based on the constrained equilibrium state theory, the nonequilibrium solvation energy is derived in the framework of the continuum model. The formula for spectral shift and vertical ionization energy are deduced for a single sphere cavity with the point charge assumption. The new model is adopted to investigate the vertical ionization for halogen atomic and molecular anions X  (X = Cl, Br, I, Cl 2 , Br 2 , I 2 ) in aqueous solution. According to the calculation using the CCSD-t/aug-cc-pVQZ method in vacuum, our final estimated vertical ionization energies in solution are very close to the experimental observations, while the traditional nonequilibrium solvation theory overestimates these vertical ionization energies. vertical ionization energy, spectral shift, constrained equilibrium state

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