Small-particle composites .2. Nonlinear optical properties

Strong fluctuations of local fields may result in very large optical nonlinearities in small-particle composites. Enhancement associated with particle clustering is found for a number of optical processes, including four-wave mixing (FWM), third-harmonic generation (THG), Raman scattering, and nonlinear refraction and absorption in Kerr media. Field fluctuations and optical nonlinear susceptibilities are especially large in fractal clusters. The enhancement of optical processes is expressed in terms of the resonant linear absorption by collective dipolar eigenmodes in a cluster, and quality factors, q, of the modes (q much greater than 1). It is shown that the susceptibility of a composite material consisting of random small-particle clusters is proportional to q(3) for Raman scattering and the Kerr optical nonlinearity, and to q(4) and q(6) for THG and FWM, respectively. For all of these processes, a spectral dependence of the effective susceptibility is found. Broad-scale numerical simulations of the optical response in small-particle composites are performed to complement the theory. The simulations are in reasonable agreement with available experimental data.