Optical Anisotropy and Dichroism

The small value of the order parameter (Equation (2.3)) and the corresponding low value of the induced optical anisotropy and dichroism [22, 67]. 

Experimental dipole moments may be used to check the validity of electrostatic calculations. In the past, dipole moments of proteins were often characterized by measurements of dielectric relaxation. More information may be obtained by measurements of the electric dichroism because these measurements provide not only the magnitude of the dipole moment but also the optical anisotropy with respect to the dipole vector. Thus, measurements of the electric dichroism provide a more rigorous test for calculations of electrostatic parameters of proteins. Using the calculations described earlier for pK s of titratable groups, one can predict dipole moments of proteins and their axes given by the principal axes of the rotational diffusion tensor and compare them with electrooptical data. ° One important aspect of comparison of computed and experimental dipole moment is that computations of dipole moments, optical anisotropy, and rotational diffusion coefficients can be used in combination with experimental electrooptical procedures to determine the long-range structure of biomacromolecular assemblies, such as the complexes of DNA and proteins described by Pbrschke et al. so... 

Figure 4.1. Time scales for rotational motions of long DNAs that contribute to the relaxation of the optical anisotropy r(t). Experimental methods used to study these motions in different time ranges are also indicated along with the authors and dates of some early work in each case. FPA, Fluorescence polarization anisotropy (Refs. 15, 18-20, and 87) TPD, transient photodichroism (Refs. 28 and 62) TEB, transient electric birefringence (Refs. 26 and 27) DDLS, depolarized dynamic light scattering (Ref. 116) TED, transient electric dichroism (Refs. 25, 115, and 130) Microscopy, time-resolved fluorescent microscopy (Ref. 176).

If the molecules stand on edge and are oriented by the dipping process, there will exist an optical anisotropy which will manifest itself in dichroism or, if the material is thick enough, in birefringence. On the other hand, if the molecules lie flat, no optical anisotropy will be shown when the material is examined by transmitted light. Thus polarising... 

The dielectric tensor describes the linear response of a material to an electric field. In many experiments, and particularly in optical rheometry, anisotropy in is the object of measurement. This anisotropy is manifested as birefringence and dichroism, two quantities that will be discussed in detail in Chapter 2. The nonlinear terms are responsible for such effects as second harmonic generation, electro-optic activity, and frequency tripling. These phenomena occur when certain criteria are met in the material properties, and at high values of field strength. 

Analogous to the definitions of linear birefringence and linear dichroism following equations (2.15) and (2.21), the form of equation (2.30) suggests the following optical anisotropies for circularly polarized light ... 

The optical measurements presented in the previous chapters can be used to either characterize local, microstractural properties or as probes of bulk responses to orientation processes. In either case, it is normally desirable to make the connection between experimental observables and their molecular or microstractural origins. The particular molecular properties that are probed will naturally depend on the physical interaction between the light and the material. This chapter explores molecular models and theories that describe these interactions and identifies the properties of complex materials that can be extracted from measurements of optical anisotropies. The presentation begins with a discussion of molecular models that are applied to polymeric materials. Using these models, optical phenomena such as birefringence, dichroism, and Rayleigh and Raman scattering are predicted. Models appropriate for particulate systems are also developed. 

In the absence of dichroism, this equation is similar in form to equation (8.27) and the extraction of the retardation and orientation angle follows the same strategy as described for the measurement of dichroism in the previous subsection. However, when dichroism cannot be neglected, the measured signal will depend on both optical anisotropies. In this case, two separate measurements will be necessary one using the optical trains of the previous section (which simply has the PSA section of the instrument replaced by (-) psA) to determine the dichroism, and a second measurement to obtain the combined... 

Conformational changes are easily followed by optical rotation (Hui and Neukom, 1964). Circular dichroism spectroscopy (CD) of polysaccharides (Morris, 1994) exploits optical anisotropy. In a CD instrumental design, the clockwise and counterclockwise rotation of two polarized beams of equal intensity, traversing a 180° path through a chiroptical medium, display a molar ellipticity maximum and minimum. CD is the differential measurement as a function of X. By CD spectroscopy, mixed interchain association rather than nonspecific incompatibility or exclusion was identified as the molecular basis of alginate-polyguluronate interaction (Thom et al., 1982). 

The isotropic signal delivers (rotation-free) information on the temporal evolution of the population numbers of the investigated vibrational transition(s). The induced dichroism is governed by the time constant ror (second-order reorientational correlation time, 1 = 2) and possibly population redistribution that may contribute to the loss of induced optical anisotropy. The zero-setting of the delay time scale (maximum overlap between pump and probing pulses) is determined by a two-photon absorption technique in independent measurements with an accuracy of better than 0.2 ps (67). 

Birefringence and dichroism represent two optical methods which can be applied to materials under flow conditions, forming the basis of Optical Rheometry [3,4]. The aim of these two techniques is to measure the anisotropy of the complex refractive index tensor n = n - i n". Birefringence is related to the anisotropy of the real part, whereas dichroism deals with the imaginary part. Recent applications of birefringence measurements to polymer melts can be foimd in Chapter III.l of the present book. 

Another mechanism responsible for the optically induced anisotropy is angular redistribution (AR) of molecules. This mechanism has been widely developed to explain photoinduced birefringence and dichroism. In most experimental cases, there is evidence of some rotation of molecules during the photoisomerization cycle (see Reference 2, for example). This rotation results in AR, because the molecules remain longer in states with lower excitation probability, and so more molecules are accumulated perpendicular to the pump polarization. The AR process is initiated by the AHB, and these two processes should be studied simultaneously in the framework of general... 

Bhnov, L. M., Kozlovsky, M. V., Ozaki, M., Skarp, K., and Yoshino, K. Photoinduced dichroism and optical anisotropy in a liquid crystalline azobenzene side-chain polymer caused by anisotropic angular distribution of trans and cis isomers. J. Appl. Phys. 84, 3860 (1998). 

Another quantity that characterizes optical anisotropy is the dichroic ratio Aj /Aj a frequently used alternative definition of the reduced linear dichroism is LD = (Ay - Aj )/(A + Aj ). In isotropic (randomly oriented) samples, there is nothing to distinguish physically between the laboratory X and y directions, so that such samples exhibit zero linear dichroism (A = A Hence, static linear dichroism studies are applicable only to oriented samples. 

One of the most interesting photoresponsive properties of azo polymers is the photoinduced birefringence and dichroism (Xie et al., 1993). The photoinduced anisotropy is caused by the disparity of the repeated trans-cis isomerization of azo chromophores under linear polarized light irradiation. The most efficient excitation occurs in the polarization direction, which can force the chromophores to continually change their orientation and to be eventually stabilized at the direction perpendicular to the polarization (Natansohn and Rochon, 2002). The effect shows potential applications in areas such as reversible optical data storage, optical switching and sensors. 

The optical anisotropy, as characterized by the difference between the absorption of IR light polarized in the directions parallel and perpendicular to the reference axis (i.e., the direction of applied strain), is known as the IR linear dichroism of the system. For a uniaxially oriented polymer system [10, 28-30], the dichroic difference, A/4(v) = y4 (v) - Ax v), is proportional to the average orientation, i.e., the second moment of the orientation distribution function, of transition dipoles (or electric-dipole transition moments) associated with the molecular vibration occurring at frequency v. If the average orientation of the transition dipoles absorbing light at frequency is in the direction parallel to the applied strain, the dichroic difference AA takes a positive value on the other hand, the IR dichroism becomes negative if the transition dipoles are perpendicularly oriented. 

The high dichroism of the crystals and their well-formed hahit can be used to align their orientation under a polarizing microscope. Of course, the optical anisotropy of the crystals as well as anisotropic reaction kinetics give rise to birefringence effects. 

A sensitive approach for the analysis of molecular structures is the measurement of rotation time constants and optical anisotropy coefficients by relaxation electrooptical methods.The experimental procedure used for electrooptical investigations is relatively simple samples are subjected to electric field pulses, and the response due to field-induced alignment or field-induced reactions is recorded by spectrophotometric techniques. In the dichroism experiments, the absorbance of polarized light is measured under electric field pulses. The measured quantity, linear dichroism (LD), means that anisotropic absorption of plane or linearly polarized light has taken place. 

Three basic types of physical phenomenon are responsible for electroopti-cal behavior of a macromolecule in solution dipole moment, diffusion coefficients, and extinction coefficients. Amplitudes and time constants depend on both the properties of the macromolecules and experimental conditions. The sum of relaxation amplitudes is related to the linear dichroism of the solution at saturation, and depends on both the electric and optical properties of the molecule under investigation. The saturating behavior of linear dichroism calculated for a pure permanent moment, a pure induced moment or a mixed orientational mechanism is traditionally used in determining electrical responses and optical anisotropy by fitting the experimental results to a theoretical curve.Pqj. molecules with effective cylindrical symmetry (regarding their orientational behavior), the optical signal observed in the experiment can be represented as a product of orientational factor, < )(j, and a limiting reduced dichroism at infinite field. 

The IR linear dichroism (i.e., the anisotropic absorption) is characterized by the integrated absorbances A and Ax measured at the band under inspection with light polarized parallel and perpendicular to the fixed reference direction, respectively. Commonly, the optical anisotropy of uniaxially oriented samples is characterized by the dichroic ratio Rdkhro = A /Ax, the dichroic difference AA = A — Ax, or by the... 

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