# How do Optically Active Compounds Rotate Plane Polarized Light?

I am not sure if this is more of a Chemistry or a Physics question, but in my Organic Chem class we discussed that chiral molecules will rotate plane polarized light. However, my professor did not discuss the mechanism at all. She also said that the only way to determine the angle of rotation was experimentally. I am really curious to know how and why this process occurs and if there is any way to calculate or even estimate the angle of rotation based on the structure of the compound.

-
To address the second part of your question, it's possible to determine the specific rotation of a compound using time-dependent density functional theory (TD-DFT) as it drops out of the first-order polarisability. Steven Bachrach has quite few blog entries on calculated specific rotations, including one of 4000 degrees by Henry Rzepa! –  Richard Terrett Oct 8 '11 at 5:57

You may start with understanding Rayleigh scattering, and then plane polarized light interacting with a simple anisotropic molecule before going onto chiral ones.

A plane polarized light wave is propagating in the direction given by the right hand rule, so let's say it's electric ($E$) field is in the $\hat{i}$ direction, the magnetic ($B$) field in the $\hat{j}$ direction so its wavevector is in the $\hat{k}$ direction.

Now let's say the light wave encounters a simple liquid crystal molecule--it's much smaller than the wavelength of the light. Forget about the chemical side-groups and other fine details, and just picture the molecule as a rod. When our light wave interacts with the rod, electrons of charge $q$ in the molecule will experience a force $Eq$ from the $E$ field of the light wave (see Lorentz force). But the electrons are bound to the molecule like a mass on a spring, so also experience a restoring force. Further, they would rather be displaced along the rod axis as opposed to away from it (the molecule's polarizability will be a tensor). This interaction of light with the electron is elastic scattering, and scattered light will have it's direction altered by the electron.

For instance, let's say that the rod is pointing at an angle $\theta$ from the $\hat{i}$ direction into the $\hat{j}$ direction. Assuming the displacement of the electon is purely along the rod's long axis, light scattered from that rod will have is polarization shifted by $\theta$.

So you don't need chiral molecules to rotate polarization of light. You could say, take some sheets of polarizing material (which is basically a sheet of rod-like molecules orientated in the same direction) and rotate them slightly with respect to each other, and these will rotate the polarization of the light passing through them.

A chiral molecular will act in a similar way--now just picture a helix of rods. Even if you have a solution of these randomly orientated, the net rotation of light will be in a given chirality. That is assuming the solution is not racemic.

If you knew the exact polarizability of your molecule of interest, you could calculate this angle of rotation. That can be a difficult thing to predict from first principles--but as one of the comments mentioned, DFT might get you that. You'd also have to know the number of your scatters, and their relative orientation, or average over all them if random. We have also assumed that the scattering is elastic--in reality there may be some inelastic scattering and absorption, and these can depend strongly on the wavelength of the light.

-
Since the anisotropic molecules are randomly oriented, the polarization shifts by each ($\theta$), will be different, making the light incident on the next molecule to have a different polarization. How then the final emergent light has a single polarization, though the individual shifts at different places (and times) were random? –  Satwik Pasani Dec 20 '13 at 4:35