Excitation energies and ionization potentials at high electric fields for molecules relevant for electrically insulating liquids

Abstract

The electric-field dependence of the molecular ionization potential and excitation energies is investigated by density-functional theory calculations. It is demonstrated that the ionization potential has a strong field dependence and decreases with increasing field. The excitation energies depend weakly on the field and the number of available excited states decreases with increasing field since the ionization potential has a stronger field dependence. Above a specific field, different for each molecule, a two-state model is obtained consisting of the electronic ground state and the ionized state. Implications for streamer propagation and electrically insulating materials are discussed.