Optical rotation

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Not to be confused with circularly polarized light.

Optical rotation or optical activity (sometimes referred to as rotary polarization) is the

rotation of the orientation of the plane of polarization about the optical axis of linearly polarized
light as it travels through certain materials. Optical activity occurs only in chiral materials, those
lacking microscopic mirror symmetry. Unlike other sources of birefringence which alter a beam's
state of polarization, optical activity can be observed in fluids. This can include gases or
solutions of chiral molecules such as sugars, molecules with helical secondary structure such as
some proteins, and also chiral liquid crystals. It can also be observed in chiral solids such as
certain crystals with a rotation between adjacent crystal planes (such as quartz) or metamaterials.
Rotation of light's plane of polarization may also occur through the Faraday effect which
involves a static magnetic field, however this is a distinct phenomenon that is not usually
classified under "optical activity."

The rotation of the plane of polarization may be either clockwise, to the right (dextrorotary — d-
rotary), or to the left (levorotary — l-rotary) depending on which stereoisomer is present (or
dominant). For instance, sucrose and camphor are d-rotary whereas cholesterol is l-rotary. For a
given substance, the angle by which the polarization of light of a specified wavelength is rotated
is proportional to the path length through the material and (for a solution) proportional to its
concentration. The rotation is not dependent on the direction of propagation, unlike the Faraday
effect where the rotation is dependent on the relative direction of the applied magnetic field.

Optical activity is measured using a polarized source and polarimeter. This is a tool particularly
used in the sugar industry to measure the sugar concentration of syrup, and generally in
chemistry to measure the concentration or enantiomeric ratio of chiral molecules in solution.
Modulation of a liquid crystal's optical activity, viewed between two sheet polarizers, is the
principle of operation of liquid-crystal displays (used in most modern televisions and computer
monitors).

Contents
  1 History
 2 Theory
 3 Areas of use
 4 See also
 5 References
 6 Further reading

History

The two asymmetric crystal forms, dextrorotatory and levorotatory, of tartaric acid.

The rotation of the orientation of linearly polarized light was first observed in 1811 in quartz by
French physicist François Jean Dominique Arago.[1] In 1820, the English astronomer Sir John
F.W. Herschel discovered that different individual quartz crystals, whose crystalline structures
are mirror images of each other (see illustration), rotate linear polarization by equal amounts but
in opposite directions.[2] Jean Baptiste Biot also observed the rotation of the axis of polarization
in certain liquids[3] and vapors of organic substances such as turpentine.[4] Simple polarimeters
have been used since this time to measure the concentrations of simple sugars, such as glucose,
in solution. In fact one name for D-glucose (the biological isomer), is dextrose, referring to the
fact that it causes linearly polarized light to rotate to the right or dexter side. In a similar manner,
levulose, more commonly known as fructose, causes the plane of polarization to rotate to the left.
Fructose is even more strongly levorotatory than glucose is dextrorotatory. Invert sugar syrup,
commercially formed by the hydrolysis of sucrose syrup to a mixture of the component simple
sugars, fructose, and glucose, gets its name from the fact that the conversion causes the direction
of rotation to "invert" from right to left.

In 1849, Louis Pasteur resolved a problem concerning the nature of tartaric acid.[5] A solution of
this compound derived from living things (to be specific, wine lees) rotates the plane of
polarization of light passing through it, but tartaric acid derived by chemical synthesis has no
such effect, even though its reactions are identical and its elemental composition is the same.
Pasteur noticed that the crystals come in two asymmetric forms that are mirror images of one
another. Sorting the crystals by hand gave two forms of the compound: Solutions of one form
rotate polarized light clockwise, while the other form rotate light counterclockwise. An equal
mix of the two has no polarizing effect on light. Pasteur deduced that the molecule in question is
asymmetric and could exist in two different forms that resemble one another as would left- and
right-hand gloves, and that the organic form of the compound consists of purely the one type.

In 1874, Jacobus Henricus van 't Hoff[6] and Joseph Achille Le Bel[7] independently proposed that
this phenomenon of optical activity in carbon compounds could be explained by assuming that
the 4 saturated chemical bonds between carbon atoms and their neighbors are directed towards
the corners of a regular tetrahedron. If the 4 neighbors are all different, then there are two
possible orderings of the neighbors around the tetrahedron, which will be mirror images of each
other. This led to a better understanding of the three-dimensional nature of molecules.

Theory
Optical activity occurs due to molecules dissolved in a fluid or due to the fluid itself only if the
molecules are one of two (or more) stereoisomers; this is known as an enantiomer. The structure
of such a molecule is such that it is not identical to its mirror image (which would be that of a
different stereoisomer, or the "opposite enantiomer"). In mathematics, this property is also
known as chirality. For instance, a metal rod is not chiral, since its appearance in a mirror is not
distinct from itself. However a screw or light bulb base (or any sort of helix) is chiral; an
ordinary right-handed screw thread, viewed in a mirror, would appear as a left-handed screw
(very uncommon) which could not possibly screw into an ordinary (right-handed) nut. A human
viewed in a mirror would have their heart on the right side, clear evidence of chirality, whereas
the mirror reflection of a doll might well be indistinguishable from the doll itself.

In order to display optical activity, a fluid must contain only one, or a preponderance of one,
stereoisomer. If two enantiomers are present in equal proportions then their effects cancel out
and no optical activity is observed; this is termed a racemic mixture. But when there is an
enantiomeric excess, more of one enantiomer than the other, the cancellation is incomplete and
optical activity is observed. Many naturally occurring molecules are present as only one
enantiomer (such as many sugars). Chiral molecules produced within the fields of organic
chemistry or inorganic chemistry are racemic unless a chiral reagent was employed in the same
reaction.

At the fundamental level, optical activity is a case of circular birefringence, and can best be
understood in that way. Whereas linear birefringence in a crystal involves a small difference in
the phase velocity of light of two different linear polarizations, circular birefringence implies a
small difference in the velocities between right and left-handed circular polarizations. Think of
one enantiomer in a solution as a large number of little helices (or screws), all right-handed, but
in random orientations. Birefringence of this sort is possible even in a fluid because the
handedness of the helices is not dependent on their orientation: even when the direction of one
helix is reversed, it still appears right handed. And circularly polarized light itself is chiral: as the
wave proceeds in one direction the electric (and magnetic) fields composing it are rotating
clockwise (or counterclockwise for the opposite circular polarization), tracing out a right (or left)
handed screw pattern in space. In addition to the bulk refractive index which substantially lowers
the phase velocity of light in any dielectric (transparent) material compared to the speed of light
(in vacuum), there is an additional interaction between the chirality of the wave and the chirality
of the molecules. Where their chiralities are the same, there will be a small additional effect on
the wave's velocity, but the opposite circular polarization will experience an opposite small effect
as its chirality is opposite that of the molecules.

The phase velocity of light in a medium is commonly expressed using the index of refraction n,
defined as the speed of light (in free space) divided by its speed in the medium. The small
difference in the refractive indices between the two circular polarizations quantifies the strength
of the optical activity,

.
The familiar rotation of the axis of linear polarization relies on the understanding that a linearly
polarized wave can as well be described as the superposition (addition) of a left and right
circularly polarized wave in equal proportion. The phase difference between these two waves is
dependent on the orientation of the linear polarization which we'll call , and their electric fields
have a relative phase difference of which then add to produce linear polarization:

where is the electric field of the net wave, while and are the two circularly polarized basis
functions (having zero phase difference). Assuming propagation in the +z direction, we could
write and in terms of their x and y components as follows:

where and are unit vectors, and i is the imaginary unit, in this case representing the 90 degree
phase shift between the x and y components that we have decomposed each circular polarization
into. As usual when dealing with phasor notation, it is understood that such quantities are to be
multiplied by and then the actual electric field at any instant is given by the real part of that
product.

Substituting these expressions for and into the equation for we obtain:

The last equation shows that the resulting vector has the x and y components in phase and
oriented exactly in the direction, as we had intended, justifying the representation of any linearly
polarized state at angle as the superposition of right and left circularly polarized components
with a relative phase difference of . Now let us assume transmission through an optically active
material which induces an additional phase difference between the right and left circularly
polarized waves of . Let us call the result of passing the original wave linearly polarized at angle
through this medium. This will apply additional phase factors of and to the right and left
circularly polarized components of :

Using similar math as above we find:

thus describing a wave linearly polarized at angle , thus rotated by relative to the incoming
wave :
We defined above the difference in the refractive indices for right and left circularly polarized
waves of . Considering propagation through a length L in such a material, there will be an
additional phase difference induced between them of (as we used above) given by:

,
where is the wavelength of the light (in vacuum). This will cause a rotation of the linear axis of
polarization by as we have shown.

In general, the refractive index depends on wavelength (see dispersion) and the differential
refractive index will also be wavelength dependent. The resulting variation in rotation with the
wavelength of the light is called optical rotatory dispersion (ORD). ORD spectra and circular
dichroism spectra are related through the Kramers–Kronig relations. Complete knowledge of one
spectrum allows the calculation of the other.

So we find that the degree of rotation depends on the color of the light (the yellow sodium D line
near 589 nm wavelength is commonly used for measurements), and is directly proportional to the
path length through the substance and the amount of circular birefringence of the material which,
for a solution, may be computed from the substance's specific rotation and its concentration in
solution.

Although optical activity is normally thought of as a property of fluids, particularly aqueous

solutions, it has also been observed in crystals such as quartz (SiO2). Although quartz has a
substantial linear birefringence, that effect is cancelled when propagation is along the optic axis.
In that case, rotation of the plane of polarization is observed due to the relative rotation between
crystal planes, thus making the crystal formally chiral as we have defined it above. The rotation
of the crystal planes can be right or left-handed, again producing opposite optical activities. On
the other hand, amorphous forms of silica such as fused quartz, like a racemic mixture of chiral
molecules, has no net optical activity since one or the other crystal structure does not dominate
the substance's internal molecular structure.

Areas of use

Sucrose solution concentration measuring experiment, demonstrating optical rotation.

For a pure substance in solution, if the color and path length are fixed and the specific rotation is
known, the observed rotation can be used to calculate the concentration. This usage makes a
polarimeter a tool of great importance to those trading in or using sugar syrups in bulk.

In the presence of an applied magnetic field, it is possible for samples of all compounds to
exhibit optical activity. A magnetic field aligned in the direction of light propagating through a
material will cause the rotation of the plane of linear polarization. This Faraday effect is one of
the first discoveries of the relationship between light and electromagnetic effects.

See also
 Cryptochirality
 Specific rotation
 Circular dichroism
 Birefringence
 Geometric phase
 Polarization
 Levorotation and dextrorotation
 Chirality (chemistry)
 Polarization rotator

References
1.

 Arago (1811) "Mémoire sur une modification remarquable qu'éprouvent les rayons lumineux
dans leur passage à travers certains corps diaphanes et sur quelques autres nouveaux phénomènes
d'optique" (Memoir on a remarkable modification that light rays experience during their passage
through certain translucent substances and on some other new optical phenomena), Mémoires de
la classe des sciences mathématiques et physiques de l'Institut Impérial de France, 1st part : 93–
134.
  Herschel, J.F.W. (1820) "On the rotation impressed by plates of rock crystal on the
planes of polarization of the rays of light, as connected with certain peculiarities in its
crystallization," Transactions of the Cambridge Philosophical Society, 1 : 43–51.
  Biot, J. B. (1815) "Phenomene de polarisation successive, observés dans des fluides
homogenes" (Phenomenon of successive polarization, observed in homogeneous fluids), Bulletin
des Sciences, par la Société Philomatique de Paris, 190–192.
  Biot (1818 & 1819) "Extrait d'un mémoire sur les rotations que certaines substances
impriment aux axes de polarisation des rayons lumineux" (Extract from a memoir on the
[optical] rotations that certain substances impress on the axes of polarization of light rays),
Annales de Chimie et de Physique, 2nd series, 9 : 372-389 ; 10 : 63-81 ; for Biot's experiments
with turpentine vapor (vapeur d'essence de térébenthine), see pp. 72-81.
  Pasteur, L. (1850) "Recherches sur les propriétés spécifiques des deux acides qui
composent l'acide racémique" (Researches on the specific properties of the two acids that
compose the racemic acid), Annales de chimie et de physique, 3rd series, 28 : 56–99 ; see also
appendix, pp. 99–117.
  van 't Hoff, J.H. (1874) "Sur les formules de structure dans l'espace" (On structural
formulas in space), Archives Néerlandaises des Sciences Exactes et Naturelles, 9 : 445–454.

1.  Le Bel, J.-A. (1874) "Sur les relations qui existent entre les formules
atomiques des corps organiques et le pouvoir rotatoire de leurs dissolutions" (On the
relations that exist between the atomic formulas of organic substances and the rotatory
power of their solutions), Bulletin de la Société Chimique de Paris, 22 : 337–347.

Further reading
 Eugene Hecht, Optics, 3rd Ed., Addison-Wesley, 1998, ISBN 0-201-30425-2
 Akhlesh Lakhtakia, Beltrami Fields in Chiral Media, World Scientific, Singapore, 1994
 A step by step tutorial on Optical Rotation
 Morrison. Robert. T, and Boyd. Robert. N, "Organic Chemistry (6th ed)". Prentice-Hall
Inc (1992).