Macroscopic-microscopic nonlinearity relationships

This result implies that the energy equipartition relationship of Eq. (2.S) applies as well as the general definitions of Chapter I. Note that for Af m the variable turns out to be coupled weakly to the thermal bath. This condition generates that time-scale separation which is indispensable for recovering an exponential time decay. To recover the standard Brownian motion we have therefore to assiune that the Brownian particle be given a macroscopic size. In the linear case, when M = w we have no chance of recovering the properties of the standard Brownian motion. In the next two sections we shall show that microscopic nonlinearity, on the contrary, may allow that the Markov characters of the standard Brownian motion be recovered with increasing temperature. 

In this paper, an overview of the origin of second-order nonlinear optical processes in molecular and thin film materials is presented. The tutorial begins with a discussion of the basic physical description of second-order nonlinear optical processes. Simple models are used to describe molecular responses and propagation characteristics of polarization and field components. A brief discussion of quantum mechanical approaches is followed by a discussion of the 2-level model and some structure property relationships are illustrated. The relationships between microscopic and macroscopic nonlinearities in crystals, polymers, and molecular assemblies are discussed. Finally, several of the more common experimental methods for determining nonlinear optical coefficients are reviewed. 

Crystals. In the discussion of equation 11, it was pointed out that the macroscopic nonlinear coefficients could be related to the microscopic ones in a relatively straightforward manner. For the hypothetical crystal shown in Figure 5, the relationship is (5)... 

Of central importance for understanding the fundamental properties of ferroelec-trics is dynamics of the crystal lattice, which is closely related to the phenomenon of ferroelectricity [1]. The soft-mode theory of displacive ferroelectrics [65] has established the relationship between the polar optical vibrational modes and the spontaneous polarization. The lowest-frequency transverse optical phonon, called the soft mode, involves the same atomic displacements as those responsible for the appearance of spontaneous polarization, and the soft mode instability at Curie temperature causes the ferroelectric phase transition. The soft-mode behavior is also related to such properties of ferroelectric materials as high dielectric constant, large piezoelectric coefficients, and dielectric nonlinearity, which are extremely important for technological applications. The Lyddane-Sachs-Teller (LST) relation connects the macroscopic dielectric constants of a material with its microscopic properties - optical phonon frequencies ... 

For symmetry reasons, the first macroscopic nonlinear coefficient is zero in unordered polymer materials. On the other hand, azo-dye polymers can exhibit very large values, which is interesting for applications in optical limiting and optical switching devices. We will consider the relationship between microscopic and macroscopic third-order susceptibilities. The most general equation for this relationship can be written as ... 

With organic compounds it is very useful to characterize the nonlinear optical response at the molecular level, and it becomes necessary to establish the relationships between the macroscopic and microscopic quantities. 

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