SAbstract. A,,sỸ E..rganic and polymer structures exhibit unusuelw arge, ultrafast second and third ( order nonlinear optical properties in a large number of structures, phase., and states. Rapid advances in the field can be achieved through further development of stable, high performance polymer structures having outstanding secondary properties as demonstrated, for example, by high performance liquid crltal polymers. For two such polymer systems, PBX and PST, third harmonic generation n~asurements show that they possess large nonresonant third order optical susceptibilLties whose origin resides in ultrafast, lossless excitations of highly charge correlated Y-electron states
IntroductionPhysical studies have demonstrated that organic and polymer structures possess unusually large, ultrafast second and third order nonlinear optical properties in a large number of material structures, phases, and states that include organic crystas, monomolecular films, polymer structures, liquid crystals and liquid crystal polymersi -. Theoretical calculations have shown that the basic origin of these properties resides in highly chage correlated excited states of the w -electron distribution comprising these structuresX' . Thesog striking properties together with demonstrations of 8 phase conjugate wave generation , optical bistability , and associative memory networks have stimulated considerable growth in research and development activities in centers throughout the world.A wide variety of potential applications in advanced optical technologies are being actively pursued that include optical signal processing and computing, image reconstruction, data storage and telecommuications.The intrinsic response time for electron excitations is ultrafast (10-14 -16-15 sec). In general, a nonlinear optical polarization in a medium involves either resonant absorptive, or non-resonant reactive, nonlinear responses. A reactive nonlinear response is due to lossless virtual optical excitations in the nonlinear medium with no net population changes or any material transformations which do occur in an absorptive response. Examples include non-resonant harmonic generation, frequency mixing, and optical Kerr effects. By far the fastest response times occur in reactive nonlinear media since reactive responses do not involve relatively slow material changes of the nonlinear medium. Moreover, among the possible virtual excitations of reactive responses, electron excitations of order 1-seconds (1 fs) are intrinsically faster than phono 2 excitations -which involve much slower nuclear displacements and vibrations of order W1 2 seconds (1 ps).For large classes of conjugated molecules and polymer structures, the remarkable property is that the nonlinear optical responses are dominated by lgles. virtual excitations of the v-electron states, especially those possessing large charge correlations.
LThis property was first demonstrated in second order responses. For example, in crystal--line solids only electronic excitations contribute to second harmonic g...