Selection rule for spectra with circular polarization

In summary, the conversation discusses the interpretation of a circular polarized electric field as the real part of a complex field and the use of different operators in determining selection rules for calculating matrix elements of the dipole operator. It is suggested to use 1st-order perturbation theory and the Wigner-Eckart theorem to simplify the process.
  • #1
forever_physicist
7
1
Hello everybody! I have a silly question that is blowing my mind.
When there is a circular polarized electric field, it can be interpreted as the real part of a complex field, for example
$$E(t) = E_0( \hat{x}+i\hat{y}) e^{-i\omega t}$$
Now, for some selection rules it is useful to calculate the matrix elements of the dipole operator in the direction of the electric field. If we use this definition that operator is
$$D_x + iD_y$$
while if we use directly the real electric field we get a different operator, that should be the correct one. Anyway, to derive the selection rules, usually this notation is used.
How can this work?
 
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  • #2
Usually one uses 1st-order perturbation theory, i.e., simply the matrix element of the dipole operator wrt. the unperturbed atomic states (Fermi's golden rule). So you can take the complex form and find the one for the real part by superposition.
 
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  • #3
In most cases where the dipole operator is non-trivial, you will end up writing the dipole matrix in the molecule frame and the electric field in the lab frame. (You make them meet with the Wigner-Eckart theorem.) So don't bother trying to guess the right coordinates for ##D## in the lab frame at the start.
 

1. What is the selection rule for spectra with circular polarization?

The selection rule for spectra with circular polarization states that only transitions between states with opposite spin angular momentum (spin-flip transitions) are allowed in circularly polarized light. This means that the change in angular momentum must be equal to +/- 1.

2. How does the selection rule for circular polarization differ from that of linear polarization?

The selection rule for circular polarization is more restrictive than that of linear polarization. In circularly polarized light, only transitions between states with opposite spin angular momentum are allowed, while in linearly polarized light, transitions between states with the same spin angular momentum are also allowed.

3. What is the significance of the selection rule for circular polarization in spectroscopy?

The selection rule for circular polarization is important in spectroscopy because it allows us to determine the spin state of a system. By analyzing the allowed transitions in circularly polarized light, we can determine the spin angular momentum of the system and gain insight into its electronic structure.

4. Can the selection rule for circular polarization be violated?

Yes, the selection rule for circular polarization can be violated in certain cases. This can occur in systems with strong spin-orbit coupling or in the presence of external magnetic fields. In these cases, transitions between states with the same spin angular momentum may be allowed in circularly polarized light.

5. How is the selection rule for circular polarization related to the parity rule?

The selection rule for circular polarization is closely related to the parity rule, which states that the parity of the initial and final states must be opposite for a transition to be allowed. In circularly polarized light, the change in angular momentum must be equal to +/- 1, which also corresponds to a change in parity. Therefore, the selection rule for circular polarization is essentially a special case of the parity rule.

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