Nuclear Magnetic Resonance Spectroscopy

Some types of atomic nuclei act as though they spin on their axis similar to the Earth. Since they are positively charged they generate an electromagnetic field just as the Earth does. So, in effect, they will act as tiny bar magnetics. Not all nuclei act this way, but fortunately both ¹H and ¹³C do have nuclear spins and will respond to this technique.

NMR Spectrometer

In the absence of an external magnetic field the direction of the spin of the nuclei will be randomly oriented (see figure below left). However, when a sample of these nuclei is place in an external magnetic field, the nuclear spins will adopt specific orientations much as a compass needle responses to the Earth’s magnetic field and aligns with it. Two possible orientations are possible, with the external field (i.e. parallel to and in the same direction as the external field) or against the field (i.e. antiparallel to the external field). See figure below right.

Figure 1: (Left) Random nuclear spin without an external magnetic field. (Right)Ordered nuclear spin in an external magnetic field

If the ordered nuclei are now subjected to EM radiation of the proper frequency the nuclei aligned with the field will absorb energy and "spin-flip" to align themselves against the field, a higher energy state. When this spin-flip occurs the nuclei are said to be in "resonance" with the field, hence the name for the technique, Nuclear Magentic Resonance or NMR.

The amount of energy, and hence the exact frequency of EM radiation required for resonance to occur is dependent on both the strength of the magnetic field applied and the type of the nuclei being studied. As the strength of the magnetic field increases the energy difference between the two spin states increases and a higher frequency (more energy) EM radiation needs to be applied to achieve a spin-flip (see image below).

Superconducting magnets can be used to produce very strong magnetic field, on the order of 21 tesla (T). Lower field strengths can also be used, in the range of 4 - 7 T. At these levels the energy required to bring the nuclei into resonance is in the MHz range and corresponds to radio wavelength energies, i.e. at a field strength of 4.7 T 200 MHz bring ¹H nuclei into resonance and 50 MHz bring ¹³C into resonance. This is considerably less energy then is required for IR spectroscopy, ~10^-4 kJ/mol versus ~5 - ~50 kJ/mol.

¹H and ¹³C are not unique in their ability to undergo NMR. All nuclei with an odd number of protons (¹H, ²H, ¹⁴N, ¹⁹F, ³¹P ...) or nuclei with an odd number of neutrons (i.e. ¹³C) show the magnetic properties required for NMR. Only nuclei with even number of both protons and neutrons (¹²C and ¹⁶O) do not have the required magnetic properties.

Exercise