Induced dipole moment nonlinear optics

Light-matter interactions can be described via an induced polarization, i.e., the induced dipole moment per unit volume. Ultrafast laser pulses, which are used in laser scanning microscopes, have high enough intensity to induce a nonlinear polarization in various materials. For intense optical electric field E, the polarization vector P can be expanded in the power series (Boyd 1992)... 

Our theoretical understanding of third-order optical nonlinearity at the microscopic level is really in its infancy. Currently no theoretical method exists which can be reliably used to predict, with reasonable computational time, molecular and polymeric structures with enhanced optical nonlinearities. The two important approaches used are the derivative method and the sum-over-states method (7,24). The derivative method is based on the power expansion of the dipole moment or energy given by Equations 3 and 4. The third-order nonlinear coefficient Y is, therefore, simply given by the fourth derivative of the energy or the third derivative of the induced dipole moment with respect to the applied field. These... 

Nonlinear optical properties arise when materials are subjected to electromagnetic radiation of very high intensity (usually from lasers). Low-intensity electromagnetic fields give a linear response for the induced dipole moment vector in a molecule ... 

Metallomesogens have been studied for their potential as nonlinear optical (NLO) materials. Such materials could find applications in the domains of opto-electronics and photonics.Nonlinearity of the optical properties means that when a molecule is placed in an intense light beam, there is no linear relationship between the induced electric dipole moment and the applied electric field, the induced dipole moment is given by Equation 2.3. 

Nonlinear optical processes occur when a medium is subjected to an intense electric field, E, such as that associated with a strong pulse of laser light. The field polarizes the medium. At the molecular level, the change of electronic density distribution creates an induced dipole moment which can be expressed as a power series ... 

To fulfill the need for understanding what structures will allow enhancement of optical nonlinearity, we have coupled ab-initio theoretical calculations of optical nonlinearity with synthesis of sequentially built and systematically derivatized model compounds, and the measurement of their optical nonlinearities. Now I would like to discuss very briefly our efforts to compare microscopic optical nonlinearities. An expression, similar to the expansion of the bulk polarization as a function of the applied field, can be written for the induced dipole moment. Naturally, the nonlinear term Y, for example, is the third derivative of the induced dipole moment with respect to the applied field. Also, using the Stark energy analysis, one can write the nonlinear terms 3 (and Y) as a sum over all excited states terms involving transition-dipoles and permanent dipoles, similar to what one does for polarizability. Consequently, the two theoretical approaches are (i) the derivative method and (ii) the sum-over-s1j tes method. We have used the derivative method at the ab-initio level. We correlate the predictions of these calculations with measurements on systematically derivatized and sequentially built model compounds. Some conclusions of our theoretical computations are as follows ... 

Obviously the larger the values of y and xYkl the higher the second- and third-order polarization created in the sample, respectively. In polymeric materials, the origin of the optical nonlinearity can be traced to the molecular constituents, and therefore, one can identify polarization due to molecular units. Accordingly, the interaction of radiation with materials can be expressed in terms of the induced molecular polarization (induced dipole moment) as follows [3] ... 

Spontaneous nonlinear as well as coherent nonlinear Raman methods are considered here. These are based on the contributions of the nonlinear part of the induced dipole moment (spontaneous effects) or the induced polarization (coherent effects) to the intensity of the frequency shifted light. In the first case, the Raman signal is generated in a spontaneous, incoherent but nonlinear optical process, whereas in the second case the Raman information is contained in a coherent laser beam whereby the nonlinear polarization acts as a coherent light source. 

In order to illustrate some of the basic aspects of the nonlinear optical response of materials, we first discuss the anliannonic oscillator model. This treatment may be viewed as the extension of the classical Lorentz model of the response of an atom or molecule to include nonlinear effects. In such models, the medium is treated as a collection of electrons bound about ion cores. Under the influence of the electric field associated with an optical wave, the ion cores move in the direction of the applied field, while the electrons are displaced in the opposite direction. These motions induce an oscillating dipole moment, which then couples back to the radiation fields. Since the ions are significantly more massive than the electrons, their motion is of secondary importance for optical frequencies and is neglected. 

The electronic structure of fluorenes and the development of their linear and nonlinear optical structure-property relationships have been the subject of intense investigation [20-22,25,30,31]. Important parameters that determine optical properties of the molecules are the magnitude and alignment of the electronic transition dipole moments [30,31]. These parameters can be obtained from ESA and absorption anisotropy spectra [32,33] using the same pump-probe laser techniques described above (see Fig. 9). A comprehensive theoretical analysis of a two beam (piunp and probe) laser experiment was performed [34], where a general case of induced saturated absorption anisotropy was considered. From this work, measurement of the absorption anisotropy of molecules in an isotropic ensemble facilitates the determination of the angle between the So Si (pump) and Si S (probe) transitions. The excited state absorption anisotropy, rabs> is expressed as [13] ... 

Linear and nonlinear optical processes are described as follows [16]. The dipole moment fA, induced in a molecule placed in an electromagnetic held with frequency of oj is given by... 

The nonlinear optical properties arise from the ability of molecules and atoms to change, in a nonlinear way, their polarization under the external forcing held (E). At the molecular level, the induced variation of the dipole moment (p) maybe developed into the electric held power series giving variation of molecule dipole moment ... 

In the above discussion, we have only considered the effects due to the CTE-CTE repulsion, which contribute to the resonant nonlinear absorption (as well as to other resonant nonlinearities) by the CTE themselves. Here, however, we want to mention a more general mechanism by which the nonlinear optical properties of media containing CTEs in the excited state can be enhanced. This influence is due to the strong static electric field arising in the vicinity of an excited CTE, If, for example, the CTE (or CT complex) static electric dipole moment is 20 Debye, at a distance of 0.5 nm it creates a field Ecte of order 107 V/cm. Such strong electric fields have to be taken into account in the calculation of the nonlinear susceptibilities, because they change the hyperpolarizabilities a, / , 7, etc. of all molecules close to the CTE. For instance, in the presence of these CTE induced static fields, the microscopic molecular hyperpolarizabilities are modified as follows... 

Chirality can also lead to certain nonlinear optical effects. In general, the dipole moment induced in a molecule by an electric field E has the components... 

The origin of nonlinear optical (NLO) properties is polarization induced by high-order terms of optical electric fields. The molecular polarization, i.e., molecular dipole moment, fi, under an electric field E Irom a laser light is generally given by... 

Combination with Static Fieids. A common technique, useful for optoelectronic devices, is to combine a monochromatic optical field with a DC or quasistatic field. This combination can lead to refractive index and absorption changes (linear or quadratic electrooptic effects and electroabsorption), or to electric-field induced second-harmonic generation (EFISH or DC-SHG, 2o) = co + co + 0) in a quasi-third-order process. In EFISH, the DC field orients the molecular dipole moments to enable or enhance the second-harmonic response of the material to the applied laser frequency. The combination of a DC field component with a single optical field is referred to as the linear electrooptic (Pockels) effect (co = co -I- 0), or the quadratic electrooptic (Kerr) effect ( = -I- 0 -I- 0). EFISH is discussed in this article, however, for the important role that it has played in the characterization of nonlinear optical materials for other applications. 

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