Organic materials for quadratic nonlinear optics generally follow the basic pattern of strongly dipolar quasi one-dimensional intramolecular charge transfer molecules organized in macroscopic crystalline or statistical polar lattices. This restriction has been lifted by the introduction of the much broader class of multipolar materials whereby efficient two- and three-dimensional molecules can be fruitfully exploited in self assembled or externally engineered multipolar macroscopic structures. At the molecular level, polarized harmonic scattering permits to evaluate the invariant irreducible components of the molecular quadratic tensor. Its anisotropy and dispersion can be accounted for by a three-quantum model in agreement with linear spectroscopy on poled samples, whereas the validity of the two-level model is restricted to one-dimensional systems. Permanent macroscopic multipolar organization can be implemented by purely optical photoinduced processes. Adequate choice of the polarization of "write" beams permits to imprint any desired symmetry pattern onto the (non)linear material. Photonic engineering thus complements and considerably broadens the more traditional scope of molecular engineering.
Simple quantum model for correlations in random one-dimensional Heisenberg antiferromagnets
