Response nonlinear

A1.6.4.4 NONLINEAR RESPONSE SYSTEMS COUPLED TO AN ENVIRONMENT (A) ECHO SPECTROSCOPY... 

If we compare the nonlinear response of = to + to) with the linear material response of we... 

Flaving now developed some of the basic notions for the macroscopic theory of nonlinear optics, we would like to discuss how the microscopic treatment of the nonlinear response of a material is handled. Wliile the classical nonlinear... 

The focus of the present chapter is the application of second-order nonlinear optics to probe surfaces and interfaces. In this section, we outline the phenomenological or macroscopic theory of SHG and SFG at the interface of centrosymmetric media. This situation corresponds, as discussed previously, to one in which the relevant nonlinear response is forbidden in the bulk media, but allowed at the interface. 

In order to describe the second-order nonlinear response from the interface of two centrosynnnetric media, the material system may be divided into tlnee regions the interface and the two bulk media. The interface is defined to be the transitional zone where the material properties—such as the electronic structure or molecular orientation of adsorbates—or the electromagnetic fields differ appreciably from the two bulk media. For most systems, this region occurs over a length scale of only a few Angstroms. With respect to the optical radiation, we can thus treat the nonlinearity of the interface as localized to a sheet of polarization. Fonnally, we can describe this sheet by a nonlinear dipole moment per unit area, -P ", which is related to a second-order bulk polarization by hy P - lx, y,r) = y. Flere z is the surface nonnal direction, and the... 

The nonlinear response of the interface may then be characterized in tenns of a surface (or interface) nonlmear susceptibility tensor. This quantity relates the applied electromagnetic fields to the induced... 

The linear and nonlinear optical responses for this problem are defined by e, 2, e and respectively, as indicated in figure Bl.5.5. In order to detemiine the nonlinear radiation, we need to introduce appropriate pump radiation fields E(m ) and (co2)- If these pump beams are well-collimated, they will give rise to well-collimated radiation emitted tlirough the surface nonlmear response. Because the nonlinear response is present only in a thin layer, phase matching [37] considerations are unimportant and nonlinear emission will be present in both transmitted and reflected directions. 

From such a treatment, we may derive explicit expressions for the nonlinear radiation in tenns of the linear and nonlinear response and the excitation conditions. For the case of nonlinear reflection, we obtain an irradiance for the radiation emitted at the nonlinear frequency of... 

The higher-order bulk contribution to the nonlmear response arises, as just mentioned, from a spatially nonlocal response in which the induced nonlinear polarization does not depend solely on the value of the fiindamental electric field at the same point. To leading order, we may represent these non-local tenns as bemg proportional to a nonlinear response incorporating a first spatial derivative of the fiindamental electric field. Such tenns conespond in the microscopic theory to the inclusion of electric-quadnipole and magnetic-dipole contributions. The fonn of these bulk contributions may be derived on the basis of synnnetry considerations. As an example of a frequently encountered situation, we indicate here the non-local polarization for SFIG in a cubic material excited by a plane wave (co) ... 

In order to achieve a reasonable signal strength from the nonlinear response of approximately one atomic monolayer at an interface, a laser source with high peak power is generally required. Conuuon sources include Q-switched ( 10 ns pulsewidth) and mode-locked ( 100 ps) Nd YAG lasers, and mode-locked ( 10 fs-1 ps) Ti sapphire lasers. Broadly tunable sources have traditionally been based on dye lasers. More recently, optical parametric oscillator/amplifier (OPO/OPA) systems are coming into widespread use for tunable sources of both visible and infrared radiation. 

Given the interest and importance of chiral molecules, there has been considerable activity in investigating die corresponding chiral surfaces [, and 70]. From the point of view of perfomiing surface and interface spectroscopy with nonlinear optics, we must first examhie the nonlinear response of tlie bulk liquid. Clearly, a chiral liquid lacks inversion synnnetry. As such, it may be expected to have a strong (dipole-allowed) second-order nonlinear response. This is indeed true in the general case of SFG [71]. For SHG, however, the pemiutation synnnetry for the last two indices of the nonlinear susceptibility tensor combined with the... 

We now consider how one extracts quantitative infonnation about die surface or interface adsorbate coverage from such SHG data. In many circumstances, it is possible to adopt a purely phenomenological approach one calibrates the nonlinear response as a fiinction of surface coverage in a preliminary set of experiments and then makes use of this calibration in subsequent investigations. Such an approach may, for example, be appropriate for studies of adsorption kinetics where the interest lies in die temporal evolution of the surface adsorbate density N. ... 

The second issue concerns molecular specificity. For a simple measurement of SHG at an arbitrary laser frequency, one caimot expect to extract infomiation of the behaviour of a system with several possible adsorbed species. To make the technique appropriate for such cases, one needs to rely on spectroscopic infomiation. In the simplest iiiiplementation, one chooses a frequency for which the nonlinear response of tlie species of interest is large or dominant. As will... 

The nonlinear response of an individual molecule depends on die orientation of the molecule with respect to the polarization of the applied and detected electric fields. The same situation prevails for an ensemble of molecules at an interface. It follows that we may gamer infonnation about molecular orientation at surfaces and interfaces by appropriate measurements of the polarization dependence of the nonlinear response, taken together with a model for the nonlinear response of the relevant molecule in a standard orientation. 

Here the ijk coordinate system represents the laboratory reference frame the primed coordinate system i j k corresponds to coordinates in the molecular system. The quantities Tj, are the matrices describing the coordinate transfomiation between the molecular and laboratory systems. In this relationship, we have neglected local-field effects and expressed the in a fomi equivalent to simnning the molecular response over all the molecules in a unit surface area (with surface density N. (For simplicity, we have omitted any contribution to not attributable to the dipolar response of the molecules. In many cases, however, it is important to measure and account for the background nonlinear response not arising from the dipolar contributions from the molecules of interest.) In equation B 1.5.44, we allow for a distribution of molecular orientations and have denoted by () the corresponding ensemble average ... 

The approach may be illustrated for molecules with a nonlinear polarizability aP dominated by a single axial component ct P., corresponding to a dominant nonlinear response from transitions along a particular... 

The influence of an applied magnetic field, as introduced in section Bl.5.2.2. is quite different from that of an applied electric field. A magnetic field may perturb the interfacial nonlinear response (and that of the weak bulk tenns), but it does not lead to any dipole-allowed bulk nonlmear response. Thus, in the presence of magnetic fields and magnetization, SHG remains a probe that is highly specific to surfaces and interfaces. It... 

In recent years, these methods have been greatly expanded and have reached a degree of reliability where they now offer some of the most accurate tools for studying excited and ionized states. In particular, the use of time-dependent variational principles have allowed the much more rigorous development of equations for energy differences and nonlinear response properties [81]. In addition, the extension of the EOM theory to include coupled-cluster reference fiuictioiis [ ] now allows one to compute excitation and ionization energies using some of the most accurate ab initio tools. 

The solution to tliis equation reflects a nonlinear response—tire kinetics n(t) are strongly dependent on the magnitude of F and/or tire initial conditions n(t = 0). 

One otlier common source of nonlinear response, singlet-triplet annihilation, is often tire reason for a discrepancy between fluorometric and absorjDtion kinetic measurements [27, 28 and 29]. 

Certain glass-ceramic materials also exhibit potentially useful electro-optic effects. These include glasses with microcrystaUites of Cd-sulfoselenides, which show a strong nonlinear response to an electric field (9), as well as glass-ceramics based on ferroelectric perovskite crystals such as niobates, titanates, or zkconates (10—12). Such crystals permit electric control of scattering and other optical properties. 

In fact, as Atluri [17] has pointed out, the hypoelastic equation of grade zero has inadequate latitude to represent realistic nonlinear response of various materials in large deformations, and it is necessary to use a hypoelastic equation of at least grade one to do so. If the grade is one, then, continuing to use Jaumann s stress rate and nondimensionalizing the stress as before, the isotropic representation (A.92) may be used in (5.112) with d = A and s = B to obtain... 

The significance of instrument band width and modulation transfer function was discussed in connection with Equation (3) to characterize the roughness of nominally smooth surfaces. The mechanical (stylus) profilometer has a nonlinear response, and, strictly speaking, has no modulation transfer function because of this. The smallest spatial wavelength which the instrument can resolve, 4nin> given in terms of the stylus radius rand the amplitude aoi the structure as... 

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