ABSTRACTThe static second hyperpolarizabilities (γ) of open-shell organic nonlinear optical (NLO) systems composed of singlet diradical molecules are investigated using ab initio molecular orbital (MO) and density functional theory (DFT) methods. It is found that neutral singlet diradical systems with intermediate diradical characters tend to enhance γ as compared to those with small and large diradical characters. This suggests that the diradical character is a novel control parameter of γ for singlet diradical systems.