The NMR Selection Rules: Understanding Allowed Spin State Transitions

In summary, the energy of a system of two interacting spin-##1/2## nuclei can be calculated using the quantum numbers ##m_1## and ##m_2##, the Larmor frequencies of each spin, and the coupling constant. The quantum number ##M## is defined as the sum of ##m_1## and ##m_2##, and only transitions with a change of ##\Delta M = \pm 1## are allowed due to conservation of angular momentum. This means that transitions where both individual spin states change, such as ##\alpha \alpha \rightarrow \beta \beta## and ##\alpha \beta \rightarrow \beta \alpha##, are not allowed since the photon required for the
  • #1
etotheipi
For simplicity I only take a system of two interacting spin-##1/2## nuclei. If the spins have quantum numbers ##m_1## and ##m_2## respectively when in a certain state, then the energy of that particular state is$$E_{m_1m_2} = m_1 v_{0,1} + m_2 v_{0,2} + m_1 m_2 J_{12}$$where ##v_{0,1}## and ##v_{0,2}## are the Larmor frequencies of the first and second spins respectively (and ##J_{12}## is the coupling constant). A quantum number for the system defined by ##M = m_1 + m_2## takes values

spin statesM
##\alpha \alpha##1
##\alpha \beta##0
##\beta \alpha##0
##\beta \beta##-1

The notes say that only transitions with ##\Delta M = \pm 1## are allowed. That is, the only allowed transitions here are ##\alpha \alpha \rightarrow \alpha \beta##, ##\alpha \alpha \rightarrow \beta \alpha##, ##\alpha \beta \rightarrow \beta \beta##, ##\beta \alpha \rightarrow \beta \beta##.

My question is, why aren't transitions where both individual spin states change allowed [i.e. ##\alpha \alpha \rightarrow \beta \beta## and ##\alpha \beta \rightarrow \beta \alpha##]?
 
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  • #2
Conservation of angular momentum. The photon required for the transition has a spin of 1.
 
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  • #3
TeethWhitener said:
Conservation of angular momentum. The photon required for the transition has a spin of 1.

Ah, of course! I hadn't considered that at all. Thanks!
 
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1. What are the NMR selection rules?

The NMR selection rules are a set of guidelines that dictate which spin state transitions are allowed in nuclear magnetic resonance (NMR) spectroscopy. These rules are based on the principles of quantum mechanics and determine which transitions are energetically favorable and therefore observable.

2. How do the selection rules affect NMR spectra?

The selection rules play a crucial role in determining the peaks and intensities observed in an NMR spectrum. Only transitions that follow the selection rules will contribute to the spectrum, while those that violate the rules will be absent. This allows for the interpretation of NMR spectra and identification of chemical compounds.

3. What are the three main NMR selection rules?

The three main NMR selection rules are the Δm = ±1 rule, the Δm = 0 rule, and the Δm = ±2 rule. The first two rules dictate that transitions can only occur between spin states that differ by one unit of angular momentum (Δm = ±1) or have the same angular momentum (Δm = 0). The Δm = ±2 rule states that transitions between spin states that differ by two units of angular momentum are highly unlikely and therefore not observed in NMR spectra.

4. How do the selection rules relate to the energy levels of nuclei?

The selection rules are based on the energy levels of nuclei, which are determined by their spin and magnetic moments. The allowed transitions are those that conserve energy and obey the rules of conservation of angular momentum. This means that only transitions between energy levels that are close in energy and have the appropriate spin states are allowed.

5. Can the selection rules be broken?

While the selection rules are generally followed in NMR spectroscopy, there are some exceptions where they can be broken. This can occur in certain special cases, such as when the sample is in a highly ordered state or when there are strong interactions between the sample and its environment. In these cases, the selection rules may not apply and transitions that would normally be forbidden may be observed in the NMR spectrum.

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