LS vs jj couplings and their selection rules

In summary, the conversation discusses the selection rules for LS and jj coupling in quantum physics and the difference between the mathematical zero and the very small transition probabilities for forbidden transitions. It is mentioned that selection rules are based on calculating the compatible electric dipole matrix element, but other moments such as electric quadrupole and magnetic dipole can also play a role. Forbidden transitions are not the result of inaccurate integrals, but rather the choice of basis set for representation.
  • #1
bentzy
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Two questions, where the 1st is related to previous discussion regarding thes couplings:
The selection rules for LS coupling is quite clear - it's based on calculating the compatible electric dipole matrix element. However, in the case of jj coupling we end up with different selection rules, which implies that the appropriate calculation here is basd on some other matrix element. What is the right (or approximate) matrix element, if not the electric dipole's ?
My 2nd question addresses Math vs Physics regarding selection rules in quantum physics. These are based on calculating the respective electric dipole matrix element & finding out under what conditions we get non-zero results. However, physically, forbidden transitions aren't strictly zero, but rather of very low probabilty. Thus, where does lie the differense between the mathematical zero (vanishing integrals) & the very minute transition probabilty ? Is it a result of the due integrals being only approximate themselves ?
 
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  • #3
The basic principle behind selection rules is angular momentum conservation. A photon carries angular momentum ##±1*\hbar## if it's right/left circularly polarized and ##0*\hbar## if linearly polarized. Hence the selection rules of ##\pm1,~0##

Forbidden transitions are not the result of inaccurate integral evaluation. They have more to do with one's conscious choice to choose one basis set of representation to represent matrix elements over another, e.g. LS coupling vs. jj coupling. If, for example, you choose a basis set appropriate to LS coupling to write down Hamiltonian matrix elements for a physical system, this does not mean that spin-orbit coupling is completely turned off. When you diagonalize the Hamiltonian to get the energy levels between which transitions may occur, you will not get pure states. There will be admixtures which will introduce non-zero transition probabilities to the (mostly) forbidden transitions.
 
  • #4
bentzy said:
Thus, where does lie the differense between the mathematical zero (vanishing integrals) & the very minute transition probabilty ?
It comes from the use of the electric dipole moment as the only coupling term. Forbidden transitions can be possible due to the electric quadrupole, magnetic dipole, etc.
 
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Related to LS vs jj couplings and their selection rules

1. What are LS and jj couplings?

LS and jj couplings are two types of coupling schemes used to describe the energy levels and transitions of atoms or molecules. LS coupling is based on the coupling of the orbital angular momentum (L) and spin angular momentum (S) of electrons, while jj coupling takes into account the individual angular momenta (j) of each electron.

2. What are the selection rules for LS and jj couplings?

The selection rules for LS coupling state that the total angular momentum (J) must change by 0 or ±1, and the change in the spin quantum number (ΔS) must be 0. For jj coupling, the selection rules are more complex and depend on the quantum numbers of the individual electrons involved in the transition.

3. How do LS and jj couplings affect spectral lines?

LS and jj couplings determine the energy levels and allowed transitions of atoms or molecules, which in turn affect the spectral lines observed. LS coupling results in simpler and more regular spectral patterns, while jj coupling leads to more complex and irregular patterns.

4. Which coupling scheme is more accurate?

Both LS and jj couplings have their strengths and weaknesses. LS coupling is more accurate for light atoms or molecules with low atomic numbers, while jj coupling is more accurate for heavy atoms or molecules with high atomic numbers. In general, jj coupling is considered to be more accurate.

5. Are there any real-life applications of LS and jj couplings?

Yes, LS and jj couplings are widely used in spectroscopy to interpret and analyze the spectral lines of atoms and molecules. They are also important in understanding the electronic structure and properties of atoms and molecules, which has implications in fields such as chemistry, physics, and materials science.

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