Finite-field method with unbiased polarizable continuum model for evaluation of the second hyperpolarizability of an open-shell singlet molecule in solvents.

The static second hyperpolarizability γ of the complexes composed of open-shell singlet 1,3-dipole molecule involving a boron atom and a water molecule in aqueous phase are investigated by the finite-field (FF) method combined with a standard polarized continuum model (PCM) and with a newly proposed unbiased PCM (UBPCM). On the basis of the comparison with the results calculated by the FF method using the full quantum and the quantum-mechanical/molecular-mechanical and molecular-dynamics (QM/MM-MD) treatments, the present FF-UBPCM method is demonstrated to remedy the artificial overestimation of the γ caused by standard FF-PCM calculations and to well reproduce the FF-QM/MM-MD and FF-full-QM results with much lower costs.

Third-order nonlinear optical properties of open-shell supermolecular systems composed of acetylene linked phenalenyl radicals.

The third-order nonlinear optical (NLO) properties, at the molecular level, the static second hyperpolarizabilities, γ, of supermolecular systems composed of phenalenyl and pyrene rings linked by acetylene units are investigated by employing the long-range corrected spin-unrestricted density functional theory, LC-UBLYP, method. The phenalenyl based superethylene, superallyl, and superbutadiene in their lowest spin states have intermediate diradical characters and exhibit larger γ values than the closed-shell pyrene based superpolyene systems. The introduction of a positive charge into the phenalenyl based superallyl radical changes the sign of γ and enhances its amplitude by a factor of 35.