Optical rotatory dispersion is the variation in the optical rotation of a substance with a change in the wavelength of light.

Optical rotatory dispersion can be used to find the absolute configuration of metal complexes. For example, when plane-polarized white light from an overhead projector is passed through a cylinder of sucrose solution, a spiral rainbow is observed perpendicular to the cylinder.[citation needed] When white light passes through a polarizer, the extent of rotation of light depends on its wavelength. Short wavelengths are rotated more than longer wavelengths. Because the wavelength of light determines its color, the variation of color with distance through the tube is observed.[citation needed] This dependence of specific rotation on wavelength is called optical rotatory dispersion. In all materials the rotation varies with wavelength. The variation is caused by two quite different phenomena. The first accounts in most cases for the majority of the variation in rotation and should not strictly be termed rotatory dispersion. It depends on the fact that optical activity is actually circular birefringence. In other words, a substance which is optically active transmits right circularly polarized light with a different velocity from left circularly polarized light. In addition to this pseudodispersion which depends on the material thickness, there is a true rotatory dispersion which depends on the variation with wavelength of the indices of refraction for right and left circularly polarized light. For wavelengths that are absorbed by the optically active sample, the two circularly polarized components will be absorbed to differing extents. This unequal absorption is known as circular dichroism. Circular dichroism causes incident linearly polarized light to become elliptically polarized. See also Absorption. Optical rotatory dispersion and circular dichroism are closely related, just as are ordinary absorption and dispersion. If the entire optical rotatory dispersion spectrum is known, the circular dichroism spectrum can be calculated, and vice versa. In order for a molecule (or crystal) to exhibit circular birefringence and circular dichroism, it must be distinguishable from its mirror image. An object that cannot be superimposed on its mirror image is said to be chiral, and optical rotatory dispersion and circular dichroism are known as chiroptical properties. Most biological molecules have one or more chiral centers and undergo enzyme-catalyzed transformations that either maintain or reverse the chirality at one or more of these centers. Still other enzymes produce new chiral centers, always with a high specificity. These properties account for the fact that optical rotatory dispersion and circular dichroism are widely used in organic and inorganic chemistry and in biochemistry. See also Enzyme; Stereochemistry. In the absence of magnetic fields, only chiral substances exhibit optical rotatory dispersion and circular dichroism. In a magnetic field, even substances that lack chirality rotate the plane of polarized light, as shown by M. Faraday. Magnetic optical rotation is known as the Faraday effect, and its wavelength dependence is known as magnetic optical rotatory dispersion. In regions of absorption, magnetic circular dichroism is observable.

Electromagnetic radiation consists of an electric (E) and magnetic (B) field that oscillate perpendicular to one another and to the propagating direction.[6], a transverse wave. While linearly polarized light occurs when the electric field vector oscillates only in one plane, circularly polarized light occurs when the direction of the electric field vector rotates about its propagation direction while the vector retains constant magnitude. At a single point in space, the circularly polarized-vector will trace out a circle over one period of the wave frequency, hence the name. The two diagrams below show the electric vectors of linearly and circularly polarized light, at one moment of time, for a range of positions; the plot of the circularly polarized electric vector forms a helix along the direction of propagation (k). For left circularly polarized light (LCP) with propagation towards the observer, the electric vector rotates counterclockwise.[2] For right circularly polarized light (RCP), the electric vector rotates clockwise.

[edit] Interaction of circularly polarized light with matter

When circularly polarized light passes through an absorbing optically active medium, the speeds between right and left polarizations differ (cL cR) as well as their wavelength (L R) and the extent to which they are absorbed (LR). Circular dichroism is the difference L- R.[4] The electric field of a light beam causes a linear displacement of charge when interacting with a

molecule (electric dipole), whereas the magnetic field of it causes a circulation of charge (magnetic dipole). These two motions combined cause an excitation of an electron in a helical motion, which includes translation and rotation and their associated operators. The experimentally determined relationship between the rotational strength (R) of a sample and the is given by

The rotational strength has also been determined theoretically,

We see from these two equations that in order to have non-zero dipole moment operators ( irreducible representation. and only chiral molecules CD active.

, the electric and magnetic

and ) must transform as the same are the only point groups where this can occur, making

Simply put, since circularly polarized light itself is "chiral", it interacts differently with chiral molecules. That is, the two types of circularly polarized light are absorbed to different extents. In a CD experiment, equal amounts of left and right circularly polarized light of a selected wavelength are alternately radiated into a (chiral) sample. One of the two polarizations is absorbed more than the other one, and this wavelength-dependent difference of absorption is measured, yielding the CD spectrum of the sample. Due to the interaction with the molecule, the electric field vector of the light traces out an elliptical path after passing through the sample. It is important that the chirality of the molecule can be conformational rather than structural. That is, for instance, a protein molecule with a helical secondary structure can have a CD that changes with changes in the conformation. [edit] Delta absorbance By definition,

where A (Delta Absorbance) is the difference between absorbance of left circularly polarized (LCP) and right circularly polarized (RCP) light (this is what is usually measured). A is a function of wavelength, so for a measurement to be meaningful the wavelength at which it was performed must be known. [edit] Molar circular dichroism It can also be expressed, by applying Beer's law, as:

where L and R are the molar extinction coefficients for LCP and RCP light, C is the molar concentration l is the path length in centimeters (cm). Then

is the molar circular dichroism. This intrinsic property is what is usually meant by the circular dichroism of the substance. Since is a function of wavelength, a molar circular dichroism value ( ) must specify the wavelength at which it is valid. [edit] Extrinsic effects on circular dichroism In many practical applications of circular dichroism (CD), as discussed below, the measured CD is not simply an intrinsic property of the molecule, but rather depends on the molecular conformation. In such a case the CD may also be a function of temperature, concentration, and the chemical environment, including solvents. In this case the reported CD value must also specify these other relevant factors in order to be meaningful. [edit] Molar ellipticity Although A is usually measured, for historical reasons most measurements are reported in degrees of ellipticity. Molar ellipticity is circular dichroism corrected for concentration. Molar circular dichroism and molar ellipticity, [], are readily interconverted by the equation:

Elliptical polarized light (violet) is composed of unequal contributions of right (blue) and left (red) circular polarized light.

This relationship is derived by defining the ellipticity of the polarization as:

where ER and EL are the magnitudes of the electric field vectors of the right-circularly and leftcircularly polarized light, respectively. When ER equals EL (when there is no difference in the absorbance of right- and left-circular polarized light), is 0 and the light is linearly polarized. When either ER or EL is equal to zero (when there is complete absorbance of the circular polarized light in one direction), is 45 and the light is circularly polarized. Generally, the circular dichroism effect is small, so tan is small and can be approximated as in radians. Since the intensity or irradiance, I, of light is proportional to the square of the electricfield vector, the ellipticity becomes:

Then by substituting for I using Beer's law in natural logarithm form:

The ellipticity can now be written as:

Since A << 1, this expression can be approximated by expanding the exponentials in a Taylor series to first-order and then discarding terms of A in comparison with unity and converting from radians to degrees:

The linear dependence of solute concentration and pathlength is removed by defining molar ellipticity as,

Then combining the last two expression with Beer's law, molar ellipticity becomes:

The units of molar ellipticity are historically (degcm2/dmol). To calculate molar ellipticity, the sample concentration (g/L), cell pathlength (cm), and the molecular weight (g/mol) must be known. If the sample is a protein, the mean residual weight (average molecular weight of the amino acids it contains) is used in place of the molecular weight, essentially treating the protein as a solution of amino acids. [edit] Mean residue ellipticity Methods for estimating secondary structure in polymers, proteins and polypeptides in particular, often require that the measured molar ellipticity spectrum be converted to a normalized value, specifically a value independent of the polymer length. Mean residue ellipticity is used for this purpose; it is simply the measured molar ellipticity of the molecule divided by the number of monomer units (residues) in the molecule.