Magnetic Circular Dichroism - Theory

Theory

Consider a system are of localized, non-interacting absorbing centers. Based on the semi-classical radiation absorption theory within the electric dipole approximation, the electric vector of the circularly polarized waves propagates in the +z direction, where + and -denote to RCP light and LCP light respectively. In this system, ω = 2nν is the circular frequency, and Ii = n – ik is the complex refractive index. As the light travels, the attenuation of the beam is expressed as

I(z) = I0exp(−2ωkz/c)

where k is the absorption coefficient of the medium in the z direction. Circular dichroism (CD) is then defined as Δk = k– – k+, and it follows the sign convention of natural optical activity. In the presence of the static, uniform external magnetic field, the Hamiltonian for the absorbing center takes the form Ĥ = Ĥ0 + Ĥ1 which is parallel to the direction of the propagation of the electric field k. Because the transition occur between the two eigenstates of Ĥ0, a and j, the absorption and the CD intensity are determined as follows:

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