Determination of the hyperpolarizability of an octopolar molecular ion by hyper-Rayleigh scattering

Abstract

The first observation to our knowledge of a second-order nonlinear optical effect in a nonpolar molecular ion is reported. Hyper-Rayleigh scattering was observed from aqueous and organic solutions of the tricyanomethanide ion [C(CN)(3)](-). Because of the absence of a dipole moment and the presence of a charge in this planar, nonpolar, but highly polarizable molecular anion with D(3h) symmetry, no electric-field-induced second-harmonic-generation experiments are possible. The experimental values for the first hyperpolarizability beta(xxx) [(7 +/- 1.5) x 10(-30) esu, independent of the solvent] are in good agreement with the results from quantum-chemical calculations.