First-order electro-optic effects

Here, the first term is referred to as the first-order electro-optic effect (Pochels effect), and the second term is referred to as the second-order electro-optic effect (Kerr effect). The coefficients rij/, and Ry/, are ternary and quaternary tensor quantities known as the Pochels constant (first-order electro-optic constant) and Kerr constant (second-order electro-optic constant), respectively. As Table 7.1.3 shows, a second-order electro-optic effect is present in materials, including isotropic materials such as glass, whereas first-order electro-optic effects are only observed in piezoelectric crystals. In Table 7.1.3, electro-optic effects are present in crystals belonging to point groups. 

Electro-optic effects in ferroelectric materials can also be dealt with by similar arguments to those used so far. For example, above the Curie temperature (about 120°C), BaTiOs belongs to a cubic system (m3m), and since it has a center of symmetry does not exhibit piezoelectric or first-order electro-optic effects. Accordingly, the electro-optic effect in this paraelectric phase is the Kerr effect. Using the polarization optical constant R in Eq. 7 instead of an electric field, it can also be expressed in terms of polarization as follows ... 

The proportionality constants a and (> are the linear polarizability and the second-order polarizability (or first hyperpolarizability), and x(1) and x<2) are the first- and second-order susceptibility. The quadratic terms (> and x<2) are related by x(2) = (V/(P) and are responsible for second-order nonlinear optical (NLO) effects such as frequency doubling (or second-harmonic generation), frequency mixing, and the electro-optic effect (or Pockels effect). These effects are schematically illustrated in Figure 9.3. In the remainder of this chapter, we will primarily focus on the process of second-harmonic generation (SHG). 

For certain macroscopic nonlinear parameters the tensor notation can be simplified due to the intrinsic symmetry of the experiment, e.g., second-harmonic generation and the linear electro-optic effect. Let us first consider SHG. The second-order contribution to the polarization is given by Eq. (9). 

The first term in Equation (14.6) is related to initial refractive indices of the medium at three primary directions, n, Uy, n. The second term refers to the linear electro-optic effect, which is known as the Pockels effect, and the third term refers to the quadratic electro-optic effect, known as the Kerr effect. Here, and Sjj are electro-optic tensors for the linear and quadratic electro-optic effects, respectively. The second-order Kerr effect is small as compared to the first-order linear effect, so it is usually neglected in the presence of linear effect. However, in crystals with centro-symmetric point groups, the linear effect vanishes and then the Kerr effect becomes dominant. 

The summation runs over repeated indices, /r, is the i-th component of the induced electric dipole moment and , are components of the applied electro-magnetic field. The coefficients aij, Pijic and Yijki are components of the linear polarizability, the first hyperpolarizability, and the second hyperpolarizability tensor, respectively. The first term on the right hand side of eq. (12) describes the linear response of the incident electric field, whereas the other terms describe the nonhnear response. The ft tensor is responsible for second order nonlinear optical effects such as second harmonic generation (SHG, frequency AotAAin, frequency mixing, optical rectification and the electro-optic effect. The ft tensor vanishes in a centrosymmetric envirorunent, so that most second-order nonlinear optical materials that have been studied so far consists of non-centrosyrmnetric, one-dimensional charge-transfer molecules. At the macroscopic level, observation of the nonlinear optical susceptibility requires that the molecular non-symmetry is preserved over the physical dimensions of the bulk stmcture. 

Two of the most important nonlinear optical (NLO) processess, electro-optic switching and second harmonic generation, are second order effects. As such, they occur in materials consisting of noncentrosymmetrically arranged molecular subunits whose polarizability contains a second order dependence on electric fields. Excluding the special cases of noncentrosymmetric but nonpolar crystals, which would be nearly impossible to design from first principles, the rational fabrication of an optimal material would result from the simultaneous maximization of the molecular second order coefficients (first hyperpolarizabilities, p) and the polar order parameters of the assembly of subunits. (1)... 

This approach is based on the introduction of molecular effective polarizabilities, i.e. molecular properties which have been modified by the combination of the two different environment effects represented in terms of cavity and reaction fields. In terms of these properties the outcome of quantum mechanical calculations can be directly compared with the outcome of the experimental measurements of the various NLO processes. The explicit expressions reported here refer to the first-order refractometric measurements and to the third-order EFISH processes, but the PCM methodology maps all the other NLO processes such as the electro-optical Kerr effect (OKE), intensity-dependent refractive index (IDRI), and others. More recently, the approach has been extended to the case of linear birefringences such as the Cotton-Mouton [21] and the Kerr effects [22] (see also the contribution to this book specifically devoted to birefringences). 

The effective electro-optic coefficient, r, of a material is related to chromophore number density, N, chromophore molecular first hyperpolarizability, P, and acentric order parameter, , by... 

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