Confusion about selection rules

In summary: Similarly, Δmj = 0 comes from the fact that the total angular momentum of an atom and photon must be the same, no matter how the atom is oriented.
  • #1
AlonsoMcLaren
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While I am reviewing my undergrad physics for qualifying exam, I became confused about the numerous selection rules.

(1) We have the selection rules for spontaneous emission in a hydrogen atom: Δl=±1 ,Δml=0,±1. This rule is the easiest to understand by evaluating <n'l'm'|z|nlm>

(2) We have the selection rules for Zeeman effect.
Δj=0,±1 ,Δmj=0,±1. I don't understand the reasons for these rules.

(3) We also have the selections rules for a helium atom where one of its electron is excited: (Modern Physics by Randy Harris, Section 8.9): Δl_total=±1, Δs_total=0, Δj_total=0,±1 (0->0 forbidden). I am totally no clue on this one.

(4) What about a hydrogen atom, without external magnetic field, but in contrast to (1), we are now considering fine structure so the good quantum numbers are n,l,j,mj?
 
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  • #2
I'm not sure what kind of answer you are looking for. Electric dipole selection rules are always based on whether ##\langle i | \hat{\mu} | f \rangle##, where ##\hat{\mu}## is the dipole operator, is zero or not. Or by "reason" do you mean the physical explanation behind the rule?
 
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  • #3
For 2, you need to know that a photon is a spin 1 particle and some basic rules of angular momentum addition. The total angular momentum of the atom and photon has to equal the total angular momentum of the excited atom.
An electric dipole only operates on the spatial (orbital) part of the wavefunction and not the spin part. When fine structure is involved, you have to consider that an eigenfunction is a superposition of up to two spatial wavefunctions (of n, l, m_l). That is,
##\psi_{nljm_j} = a \psi(x)_{nl,m_l=m_j-1/2} \psi_{m_s=+1/2} + b \psi(x)_{nl,m_l=m_j+1/2} \psi_{m_s=-1/2}##
So the problem including fine structure just reduces to the sum of some calculations with no fine structure (approximately).
 
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  • #4
DrClaude said:
I'm not sure what kind of answer you are looking for. Electric dipole selection rules are always based on whether ##\langle i | \hat{mu} | f \rangle##, where ##\hat{mu}## is the dipole operator, is zero or not. Or by "reason" do you mean the physical explanation behind the rule?

Yes I do mean the physical reasons behind these rules
 
  • #5
The photon is a spin-1 particle, meaning that it has ħ angular momentum. Conservation of angular momentum is responsible for the selection rule Δl = ±1, and conservation of the projection of angular momentum for Δml = 0, ±1 (corresponding to π, σ+, and σ- polarized light).

Δs = 0 because the EM field doesn't couple to spin.

The rules for Δj and Δmj follow from the above rules for orbital angular momentum and spin. Δj = 0 is a bit more complicated to explain, but it comes from the fact that even though Δl = ±1, you can modify the orientations of l and s such that the resulting j vector is the same length, but this does not work if j = 0, so no 0 → 0 transition.
 

Related to Confusion about selection rules

1. What are selection rules in science?

Selection rules are a set of guidelines that determine which transitions are allowed between energy levels in an atom or molecule. These rules are based on the conservation of energy, angular momentum, and parity.

2. How do selection rules affect spectral lines?

Selection rules limit the number of possible transitions between energy levels, resulting in a specific pattern of spectral lines. This pattern can be used to identify elements or molecules present in a sample.

3. What is the difference between allowed and forbidden transitions?

Allowed transitions follow the selection rules and are observed as spectral lines, while forbidden transitions violate the selection rules and are not observed. However, forbidden transitions can occur under certain conditions, such as in highly excited atoms or in the presence of external perturbations.

4. Why are selection rules important in spectroscopy?

Selection rules provide a framework for interpreting spectral data and understanding the electronic structure of atoms and molecules. They also allow for the identification of unknown substances based on their unique spectral patterns.

5. How do selection rules relate to the quantum mechanical model?

The selection rules are a consequence of the quantum mechanical model, specifically the conservation of energy and angular momentum. The model helps to explain the observed patterns of spectral lines and the allowed transitions between energy levels in atoms and molecules.

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