Trying to Understand Molecular Excited States Notation

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SUMMARY

This discussion focuses on the notation used to describe molecular excited states, specifically for nitrogen dioxide as detailed in the paper by V.M. Donnelly et al. The transition notation \widetilde{A}^{2}B_{2} \leftarrow \widetilde{X}^{2}A_{1} indicates a transition from the \widetilde{X}^{2}A_{1} state to the \widetilde{A}^{2}B_{2} state, with the arrow direction denoting the transition process. The letters A and B refer to irreducible representations of the C_{2v} symmetry group, while the superscript "2" signifies a total spin of s=1/2, indicating two possible spin orientations. Understanding this nomenclature is crucial for interpreting molecular spectroscopy and related phenomena.

PREREQUISITES
  • Familiarity with molecular symmetry groups, specifically C_{2v}.
  • Understanding of electronic wavefunctions and their representations.
  • Knowledge of spin states in quantum mechanics.
  • Basic principles of laser-induced fluorescence.
NEXT STEPS
  • Research the concept of irreducible representations in molecular symmetry.
  • Study the implications of spin states in electronic transitions.
  • Explore the role of laser-induced fluorescence in molecular spectroscopy.
  • Read the referenced articles for deeper insights into molecular excited states.
USEFUL FOR

PhD students in engineering, chemists studying molecular spectroscopy, and researchers interested in the electronic properties of nitrogen dioxide and similar molecules.

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Hey guys, I'm an engineering PhD student, and I'm doing some work with laser-induced fluorescence. At the moment, I'm trying to understand some notation about the excited states of nitrogen dioxide. One of the papers I'm looking at, V.M. Donnelly, et al. J. Chem. Phys. 71, 659 (1979), is saying that the transition I'm inducing is \widetilde{A}^{2}B_{2} \leftarrow \widetilde{X}^{2}A_{1}. I'm not entirely sure what any of that means. I assume it's saying that I'm transitioning from the \widetilde{X}^{2}A_{1} state to the \widetilde{A}^{2}B_{2} state, but why the arrow points right to left, I'm not sure. More importantly, I'm not sure what any of the numbers or letters refer to, and what the tilda's mean. I assume some information about the rotational and vibrational states are given (that that's what I'd really like to know), but not knowing the nomenclature, I'm not sure how to read that transition. I'd appreciate it if someone could point me in the right direction. Thanks.
 
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A_1 and B_2 refer to the irreducible representations of the symmetry group of the molecule (C_{2v}) spanned by the electronic wavefunction. The superscript "2" means that the total spin of the electronic wavefunction is s=1/2 (Hence there are 2s+1=2 possible orientations of the spin. I. e., the spin of the single unpaired electron may either point up (m_s=+1/2 or down m_s=-1/2). No idea about the tilde. The states of a given symmetry are usually enumerated A, B, ...X , with A being energetically lowest, then B etc.
Maybe you can learn something from this article:
http://www.sciencemag.org/content/334/6053/208.abstract
or this one:
http://onlinelibrary.wiley.com/doi/10.1002/9780470142813.ch2/summary
 
Last edited:
I think I'm starting to understand. Thanks.
 

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