Why Does Electron Spin Play No Role in NMR?

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Discussion Overview

The discussion revolves around the role of electron spin in nuclear magnetic resonance (NMR), particularly why it is often considered negligible in the basic description of NMR despite the presence of electrons in hydrogen. Participants explore the interactions between nuclear and electronic spins, the concept of resonance, and the conditions under which NMR is typically conducted.

Discussion Character

  • Technical explanation
  • Conceptual clarification
  • Debate/contested

Main Points Raised

  • Some participants note that while electron spin should couple with proton spin, in standard NMR, the electron's role is minimal due to the focus on nuclear transitions.
  • One participant explains that the resonance frequency for electronic transitions is typically outside the detection bandwidth used for NMR.
  • Another point raised is that the electron magnetic moment differs significantly from that of protons due to the mass difference, affecting resonance characteristics.
  • Participants discuss the importance of coupling spins in ground state energy calculations, but emphasize that in the presence of an external field, the interaction with the nucleus is minimal when flipping nuclear spins.
  • There is mention of the 21-cm line related to the proton magnetic moment and the atomic 1s electron, indicating a resonance that exists but is not the focus of NMR.
  • One participant highlights that NMR is typically conducted in diamagnetic media where electronic spins are coupled into a singlet state, which does not couple to the nucleus's magnetic moment.

Areas of Agreement / Disagreement

Participants express various viewpoints on the role of electron spin in NMR, with some agreeing on its minimal impact in typical scenarios, while others raise points about the conditions under which electron spin might be relevant. The discussion remains unresolved regarding the extent of electron spin's influence in different contexts.

Contextual Notes

Participants acknowledge that the energy required to break up an electronic singlet state is significant, typically beyond what can be achieved with radio frequency radiation used in NMR.

blue2script
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Hi all!
I only have a short question concerning nuclear magnetic resonance: the basic principle is that we apply an external magnetic field, the protons (the core of H^1) is split into two energy levels (depending on the alignment of its spin) and we can apply an external high-frequency pulse to do the usual stuff.

Now, there are also electrons in hydrogen. Normally the spin of the proton and the spin of the electron should couple. However, in the normal basic description of NMR the electron plays no role at all. Why is that?

Thank you very much in advance!
Blue2script
 
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blue2script said:
Hi all!
I only have a short question concerning nuclear magnetic resonance: the basic principle is that we apply an external magnetic field, the protons (the core of H^1) is split into two energy levels (depending on the alignment of its spin) and we can apply an external high-frequency pulse to do the usual stuff.

Now, there are also electrons in hydrogen. Normally the spin of the proton and the spin of the electron should couple. However, in the normal basic description of NMR the electron plays no role at all. Why is that?

Thank you very much in advance!
Blue2script

That's why there is this "resonance" part in the name. You "tune" into the exact frequency that corresponds to the nuclear transition. The electronic transition would probably be quite far off the bandwidth of what you are detecting.

BTW, there is also the NMR equivalent for electron, called electron paramagnetic resonance, or electron spin resonance. In that case, you tune out the nuclear resonance and just zero in on the frequency corresponding to the electrons.

Zz.
 
ZapperZ said:
That's why there is this "resonance" part in the name. You "tune" into the exact frequency that corresponds to the nuclear transition. The electronic transition would probably be quite far off the bandwidth of what you are detecting.
Indeed, the electron magnetic moment is quite different due to lighter mass: µ ∝ 1/m.
The resonance is different for different nuclei. This is how one distinguishes (measures) the atomic content of the sample in question.
 
blue2script said:
Now, there are also electrons in hydrogen. Normally the spin of the proton and the spin of the electron should couple. However, in the normal basic description of NMR the electron plays no role at all. Why is that?
Coupling spins is important in the ground state energy calculations. But in presence of an external field we have additional interaction Hamiltonians for each spin. We may affect the atom by acting on a particular atomic particle (subsystem). Of course the atomic state changes but too little in case of nucleus spin flipping. That is important in a sense of non-destructive intervention (interaction).
 
There is also the resonance of the proton magnetic moment in the magnetic moment of the atomic 1s electron, known either as the 21-cm line or the 1420-MHz line.
Bob S
 
Right, but it is an atomic resonance, a whole system resonance (a proper frequency, no external field involved).
 
Last edited:
An important point, which has not been mentioned till now, is that NMR is usually only performed in diamagnetic media, where all electronic spins are coupled into a singlet.
By definition, the magnetic momentum of a singlet is vanishing so that it won't couple to the magnetic moment of the nucleus.
The energy necessary to break up an electronic singlet state is typically that of an electronic bond, so that it is not possible with radio frequency radiation.
 

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