Electronic Structure of Open-Shell Singlet Molecules: Diradical Character Viewpoint

Abstract

This chapter theoretically explains the electronic structures of open-shell singlet systems with a wide range of open-shell (diradical) characters. The definition of diradical character and its correlation to the excitation energies, transition properties, and dipole moment differences are described based on the valence configuration interaction scheme using a two-site model with two electrons in two active orbitals. The linear and nonlinear optical properties for various polycyclic aromatic hydrocarbons with open-shell character are also discussed as a function of diradical character.