Selection Rules for a Diatomic Molecule?

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Discussion Overview

The discussion revolves around the selection rules for electronic transitions in diatomic molecules, specifically focusing on the confusion surrounding the rules ΔΛ=0 and ΔΛ=0, ±1 as presented in various texts. Participants are exploring theoretical aspects and clarifying concepts related to molecular spectra.

Discussion Character

  • Exploratory
  • Technical explanation
  • Debate/contested

Main Points Raised

  • One participant expresses confusion regarding the selection rules stated in Bransden and Joachain's book, noting a contradiction between ΔΛ=0 and ΔΛ=0, ±1.
  • Another participant questions the relevance of ΔΛ in the context of pure rotational spectra as discussed in the same book.
  • A participant suggests that the selection rules may depend on whether one of the λ values is zero or not, indicating a need for separation in analysis.
  • Another participant emphasizes that the selection rules for ΔK differ depending on whether λ is zero or not.
  • A later post references classic texts by Herzberg and Townes & Scawlow as providing definitive discussions on selection rules, suggesting that these may clarify the confusion.

Areas of Agreement / Disagreement

Participants do not reach a consensus on the correct selection rules, with multiple competing views and interpretations of the texts presented. The discussion remains unresolved regarding the application of the rules.

Contextual Notes

There are limitations in the discussion regarding the assumptions made about the contexts in which the selection rules apply, and the specific definitions of terms like λ and K are not fully clarified.

Sebacide
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Hello!
I have a question about selection rules and electronic transitions of a diatomic molecule: I can't find a good explanation about that, and there's so much confusion about the right rules to use.
I studied that on Bransden-Joachain's "Physics of atoms and molecules", but there (to whom have the book, paragraphs 11.1 and 11.3 of 2nd edition) is said that diatomic molecules are forced to have a transition with ΔΛ=0, and, some pages on, that there is a rule ΔΛ=0,+-1; so, which is the right one?
Surely they are referred to different situations, but it is not explained very clearly.
Thanks for the answers!
 
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I don't really understand what Bransden and Joachain are saying in 11.1. They are discussing pure rotational spectra, so I don't see why they invoke ##\Delta \Lambda##.

In any case, 11.3 is correct and ##\Delta \Lambda = 0, \pm 1##.
 
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Hi, thank you for your help: I thought the same, but during class it was mentioned the ##\Delta \Lambda=0## only.
So, if I have to describe the possible transition between two fixed electonic states, I have to separate the case in which one of the two lamdas is not zero and the one they are zero?
 
Sebacide said:
Hi, thank you for your help: I thought the same, but during class it was mentioned the ##\Delta \Lambda=0## only.
So, if I have to describe the possible transition between two fixed electonic states, I have to separate the case in which one of the two lamdas is not zero and the one they are zero?
The selection rules on ##\Delta K## is not the same for ##\Lambda = 0 \leftrightarrow \Lambda = 0## than for ##\Lambda \neq 0 \leftrightarrow \Lambda \neq 0##
 
Sebacide said:
I have a question about selection rules and electronic transitions of a diatomic molecule: I can't find a good explanation about that, and there's so much confusion about the right rules to use.
The following books provide definitive discussions of the selection rules:

1. G. Herzberg, "Molecular Spectra and Molecular Structure. Volume I: Spectra of Diatomic Molecules. Second Edition" D. Van Nostrand, 1950.

2. C. H. Townes and A. L. Scawlow, "Microwave Spectroscopy", McGraw Hill, 1955.

While not new books, they are classic discussions of the fundamental concepts.
 

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