Polarizer dichroic

The circular polarized dichroic ratio D is represented in the following equation. 

The external reflection of infrared radiation can be used to characterize the thickness and orientation of adsorbates on metal surfaces. Buontempo and Rice [153-155] have recently extended this technique to molecules at dielectric surfaces, including Langmuir monolayers at the air-water interface. Analysis of the dichroic ratio, the ratio of reflectivity parallel to the plane of incidence (p-polarization) to that perpendicular to it (.r-polarization) allows evaluation of the molecular orientation in terms of a tilt angle and rotation around the backbone [153]. An example of the p-polarized reflection spectrum for stearyl alcohol is shown in Fig. IV-13. Unfortunately, quantitative analysis of the experimental measurements of the antisymmetric CH2 stretch for heneicosanol [153,155] stearly alcohol [154] and tetracosanoic [156] monolayers is made difflcult by the scatter in the IR peak heights. 

In order to develop the dyes for these fields, characteristics of known dyes have been re-examined, and some anthraquinone dyes have been found usable. One example of use is in thermal-transfer recording where the sublimation properties of disperse dyes are appHed. Anthraquinone compounds have also been found to be usehil dichroic dyes for guest-host Hquid crystal displays when the substituents are properly selected to have high order parameters. These dichroic dyes can be used for polarizer films of LCD systems as well. Anthraquinone derivatives that absorb in the near-infrared region have also been discovered, which may be appHcable in semiconductor laser recording. 

Intermediate methods include the earliest procedure based on Stein s equation [33] and one based on Samuels equation [34]. Among the direct methods is an IR spectroscopic method based on the measurement of the dichroic ratio (R), of amorphous absorption bands. In the investigations [35], the amorphous bands 898 cm" and 1368 cm", for which the angles of transition moment are a898 = 39 and aneg = 80 , respectively, were used. Other methods are spectroscopy of polarized fluorescent radiation [35,36], measurement of color di-... 

Plastics are suitable for most optical applications that utilize transparent materials, including color carriers. Color filters have all types of standard transmission characteristics that can be made and, because of the uniqueness of the plastic structure, a large number of dichroic and trichroic materials are possible that have different colors when viewed from different angles. One application for this is in polarizing filters. 

Figure 4.6 Block diagram of the apparatus for the fluorescence depolarization measurement. The dashed and solid arrows indicate the light paths ofthe excitation pulse and the fluorescence from the sample. OBJ microscope objective, M mirror, L lens, DM dichroic mirror, LP long-pass filter, PH pin-hole, PBS polarizing beam splitter, P polarizer, PMT photomultiplier.

Normal incidence transmission IRLD measurements are used to study thin films (typically 100 pm thickness and less, depending on the molar extinction coefficient of the bands) with in-plane uniaxial orientation. Two spectra are recorded sequentially with the radiation polarized parallel (p) and perpendicular (s) to the principal (machine) direction of the sample. The order parameter of the transition moment of the studied vibration is calculated from either the dichroic ratio (R — Ap/As) or the dichroic difference (AA = Ap—As) as ... 

The parameters K1/ K2/ and K3 are defined by the refractive indices of the crystal and sample and by the incidence angle [32]. If the sample has uniaxial symmetry, only two polarized spectra are necessary to characterize the orientation. If the optical axis is along the plane of the sample, such as for stretched polymer films, only the two s-polarized spectra are needed to determine kz and kx. These are then used to calculate a dichroic ratio or a P2) value with Equation (25) (replacing absorbance with absorption index). In contrast, a uniaxial sample with its optical axis perpendicular to the crystal surface requires the acquisition of spectra with both p- and s-polarizations, but the Z- and X-axes are now equivalent. This approach was used, through dichroic ratio measurements, to monitor the orientation of polymer chains at various depths during the drying of latex [33]. This type of symmetry is often encountered in non-polymeric samples, for instance, in ultrathin films of lipids or self-assembled monolayers. 

A more complex but faster and more sensitive approach is polarization modulation (PM) IRLD. For such experiments, a photoelastic modulator is used to modulate the polarization state of the incident radiation at about 100 kHz. The detected signal is the sum of the low-frequency intensity modulation with a high-frequency modulation that depends on the orientation of the sample. After appropriate signal filtering, demodulation, and calibration [41], a dichroic difference spectrum can be directly obtained in a single scan. This improves the time resolution to 400 ms, prevents artifacts due to relaxation between measurements, and improves sensitivity for weakly oriented samples. However, structural information can be lost since individual polarized spectra are not recorded. Pezolet and coworkers have used this approach to study the deformation and relaxation in various homopolymers, copolymers, and polymer blends [15,42,43]. For instance, Figure 7 shows the relaxation curves determined in situ for miscible blends of PS and PVME [42]. The (P2) values were determined... 

Based on experiments with linearly polarized light, Mayer also concluded that the photoreceptor is arranged in a dichroic fashion close to the cell wall. The electrical dipole moment for the absorption of bluelight lies parallel to the cell wall, but is probably random with respect to the normal of the cell wall. In the first experiment, the cells were irradiated with bright light. Clearly, the chloroplasts separate from the walls, which are parallel to the -vector and exhibit a banded pattern (Fig. 17, left). However, in weak polarized light the chloroplasts tended to move close to those walls parallel to the -vector (Fig. 17, right). 

The optical transition moments for vibrational or electronic transitions between defect states have specific orientations with respect to the defect coordinates. The absorption strength of polarized light for each of the differently oriented centers is proportional to the square of the component of the transition moment that is along the polarization direction. Hence, a stress-induced redistribution of the defects among their different orientations will be detected as an anisotropy in the polarized optical absorption. A convenient measure of the anisotropy is the dichroic ratio, defined as... 

The out-of-plane orientation of chromophores can be more easily controlled in LB films as compared with the in-plane orientation. Many chromophores are known to show anisotropic orientation in the surface normal direction. The molecular structure of chromophores and their position in amphiphile molecules, the surface pressure, the subphase conditions are among those affect their out-of-plane orientation. The out-of-plane orientation has been studied by dichroic ratio at 45° incidence, absorbance ratio at normal and 45° incidence, and incident angle dependence of p-polarized absorption [3,4,27,33-41]. The evaluation of the out-of-plane orientation in LB films is given below using amphipathic porphyrin (AMP) as an example [5,10,12]. 

Further, planar orientation of PPV chains in the film plane was demonstrated from the linear dichroism dichroic ratio Ap/As decreased from 2.1 to 1.2 when the incident angle of polarized light increased from 0° to 45°, where Ap and As... 

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