Raman scattered circular polarization

Within the harmonic approximation, the Raman, ROA [for a naturally polarized incident light (n) in the scattered circularly polarized (SCP) scheme] [26-28], IR, and VCD [29-32] intensities associated with the pth vibrational normal mode respectively read ... 

Spencer KM, Freedman TB, Nafie LA. Scattered circular polarization Raman optical activity. Chem. Phys. Lett. 1988 149(4) 367-374. 

For a circularly polarized light experiment, one can measure the cross sections for either right (r) or left (1) polarized scattered light. Suppose that right polarized light is made incident on a Raman active sample. The general expressions for the Raman cross sections are [176]... 

Fig. 1. The basic ROA experiment measures a small difference in the intensity of Raman scattering from chiral molecules in right- and left-circularly polarized incident light. Reprinted from Barron et al., 2000, Prog. Biophys. Mol. Biol. 73,1-49, with permission from Elsevier Science.

Probing Metalloproteins Electronic absorption spectroscopy of copper proteins, 226, 1 electronic absorption spectroscopy of nonheme iron proteins, 226, 33 cobalt as probe and label of proteins, 226, 52 biochemical and spectroscopic probes of mercury(ii) coordination environments in proteins, 226, 71 low-temperature optical spectroscopy metalloprotein structure and dynamics, 226, 97 nanosecond transient absorption spectroscopy, 226, 119 nanosecond time-resolved absorption and polarization dichroism spectroscopies, 226, 147 real-time spectroscopic techniques for probing conformational dynamics of heme proteins, 226, 177 variable-temperature magnetic circular dichroism, 226, 199 linear dichroism, 226, 232 infrared spectroscopy, 226, 259 Fourier transform infrared spectroscopy, 226, 289 infrared circular dichroism, 226, 306 Raman and resonance Raman spectroscopy, 226, 319 protein structure from ultraviolet resonance Raman spectroscopy, 226, 374 single-crystal micro-Raman spectroscopy, 226, 397 nanosecond time-resolved resonance Raman spectroscopy, 226, 409 techniques for obtaining resonance Raman spectra of metalloproteins, 226, 431 Raman optical activity, 226, 470 surface-enhanced resonance Raman scattering, 226, 482 luminescence... 

The other form of optical activity in vibrational transitions is known as Raman optical activity (ROA). Here, also, one measures an intensity difference for left compared to right circularly polarized incident radiation however, optical activity in light scattering has no direct analog in electronic spectroscopy. ROA was first measured by Laurence Barron, A. D. Buckingham, and M. P. Bogaard in 1973 (9) and several reviews of the subject have since appeared (10-14). 

The measurement of vibrational optical activity requires the optimization of signal quality, since the experimental intensities are between three and six orders of magnitude smaller than the parent IR absorption or Raman scattering intensities. To date all successful measurements have employed the principles of modulation spectroscopy so as to overcome short-term instabilities and noise and thereby to measure VOA intensities accurately. In this approach, the polarization of the incident radiation is modulated between left and tight circular states and the difference intensity, averaged over many modulation cycles, is retained. In spite of this common basis, there are major differences in measurement technique and instrumentation between VCD and ROA consequently, the basic experimental methodology of these two techniques will be described separately. 

Abstract Now an incisive probe of biomolecular structure, Raman optical activity (ROA) measures a small difference in Raman scattering from chiral molecules in right- and left-circularly polarized light. As ROA spectra measure vibrational optical activity, they contain highly informative band structures sensitive to the secondary and tertiary structures of proteins, nucleic acids, viruses and carbohydrates as well as the absolute configurations of small molecules. In this review we present a survey of recent studies on biomolecular structure and dynamics using ROA and also a discussion of future applications of this powerful new technique in biomedical research. 

Fig. 7.1. Two equivalent ROA experiments involving Stokes vibrational Raman scattering at angular frequency oj — ojv in incident light of angular frequency oj far from resonance, a The ICP ROA experiment measures JR - JL, where JR and JL are the scattered intensities (shown here as unpolarized) in right- and left-circularly polarized incident light, respectively, b The SCP ROA experiment measures hi-h., where Jr and JL are the intensities of the right- and left-circularly polarized components, respectively, of the scattered light using incident light of fixed polarization (shown here as unpolarized)...

As described above, there are two forms of vibrational optical activity, one derived from infrared absorption and the other from Raman scattering. Both forms involve the differential response of a molecule to the modulation of polarization of the interacting radiation between right and left circularly polarized states. In the case of infrared absorption, VCD is defined as die differential absorbance for left minus that for right circularly polarized infrared radiation. This is expressed by the relation ... 

Scattering and other forms of spectroscopy Rely on the fact that electromagnetic radiation has other interactions with matter beyond that of simple absorption and emission. These interactions generate other measurable quantities such as scattering of polarized light (e.g. circular dichroism), and changes of spectral features of chemical bonds (e.g. Raman spectroscopy). 

Nafie (1992) has given a review about the latest VOA instrumentation. Until 1988, the only measured form of ROA was incident circular polarisation (ICP) ROA, but as the process observed in Raman spectroscopy is a two-photon process, there are four possibilities for measuring Raman optical activity. ICP ROA is the unpolarized measurement of the Raman radiation emitted upon excitation with alternating right and left circularly polarized light. It is shown in Fig. 6.3-12, following the sketches of Nafie. As the first of the other possibilities scattered circular polarisation (SCP) ROA was measured. This... 

The occurrence of Raman scattering is connected to the change in polarizability during the transition of the molecule from one vibrational state to the other. Circular polarization ROA arises from interference of the electric dipole electric dipole polarizability tensor with the electric dipole - magnetic dipole and the electric dipole electric quadrupole optical activity tensors. Due to limited space, no rigorous derivation of the theory will be given here, but only the most important results shall be shown. 

Figure 8 Schematic layout of a typical 90° Raman depolarization experiment showing the positions of the polarization analyzer and the scrambler. The analyzer may simply be a polaroid sheet, which can be rotated by 90° to allow the parallel ( ) and perpendicular ( ) components of the scattered light to pass through to the detector. The function of a scrambler is to change linear into circular polarization of the light entering the Raman spectrometer slit in order to avoid measurement errors due to the variable spectrometer transmittance of the light polarized in different directions...

Raman optical activity (RO A) Due to molecular chirality there is a difference in the intensity of Raman scattered right and left circularly polarized light. Raman optical activity (ROA) is a vibrational spectroscopic technique that is reliant on this difference and the spectrum of intensity differences recorded over a range of wavenumbers reveals information about chiral centers within a sample molecule. It is a useful probe to study biomolecular structures and their behavior in aqueous solution especially those of proteins, nucleic acids, carbohydrates, and viruses. The information obtained is in realistic conditions... 

Raman Optical Activity The Raman optical activity (ROA) effect is the differential scattering of left- or right-circularly polarized light by a chiral substrate where chirality is studied through Raman spectroscopy. 

This article reviews all the published work concerned with the study of vibrational optical activity in chiral molecules from measurements of a small difference in the intensity of Raman scattering in right and left circularly polarized incident light. The history and basic theory are described briefly, followed by an account of the instrumentation and the precautions that must be observed in order to suppress spurious signals. The various theories that have been proposed in order to relate stereochemical features to the observations are then outlined, this being followed by a survey of all reported Raman optical activity spectra. 

The Raman approach to vibrational optical activity is based on measurement of a small difference in the intensity of Raman-scattered light from chiral molecules in right and left circularly polarized incident light, and several reviews have appeared previously1 -S). However, another review is now timely because important experimental and theoretical developments have since brought Raman optical activity (ROA) to a new level of maturity. 

Hug and Surbeck 35) have proposed the use of Ada. = daL — daR, the difference of the Raman differential scattering cross sections in left and right circularly polarized incident light. This is the Raman equivalent of the circular dichroism Ae = el — eR, where s is the decadic molar extinction coefficient and, unlike the measured (but not the theoretical) IR — IL which depends on both sample and instrumental factors, is solely a molecular parameter. They introduced a chirality number q defined by... 

Chiral objects absorb left and right circularly polarized light to slightly different extents. Tltis phenomenon of circular dichroism [1] became the basis of the most widespread practical chiroptical method in the past few decades. There are some other chiroptical methods based on the interaction of chiral matter with circularly polarized light Optical rotatory dispersion is based on the analogous difference in refraction. Raman optical activity measures differences in scattered light, and circularly polarized luminescence deals with the difference in emission. 

Raman optical activity (ROA) provides a means for studying vibrational transitions via differential scattering of right- and left-circular polarized light ... 

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