NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY (NMR)

 Spectroscopic technique that relies on the magnetic properties of the atomic nucleus.

 Magnetic nuclei possess nuclear spin (I) whose magnitude is quantized in units of h/2.
 When placed in a strong magnetic field, certain nuclei which possess spin resonate at a
characteristic frequency in the radio frequency range of the electromagnetic spectrum and
they adopt one of the small number of allowed orientations of different energy.
 They include 13C, 15N, 31P and 1H among others.
 The spinning nuclei also possess charge and the motion of this charge gives rise to an
associated magnetic moment,  such that:

=       

wherethe term  is the magnetogyric ratio, which is constant for any given nuclide. The spin
angular momentum (I) has values in units of h/2therefore;

𝛾𝐼ℎ
= 1.2
2𝜋
The energy of interaction is simply proportional to the nuclear moment and the applied field
thus;

𝛾ℎ
E= - mIB 1.3
2𝜋

where B is the applied field.

When placed in a strong magnetic field, the allowed transitions are between adjacent energy
levels (i.e. m = ±1) and therefore;
𝛾ℎ
2𝜋B 1.4

For detection of this transition energy, radiation given by E = his applied thus the
fundamental resonance condition for all NMR experiments should be;
 𝛾B
 = 2𝜋 1.5

This means, for obtaining NMR spectra either the field, B or the frequency may be varied. Now
because the magnetic field experienced by a nucleus in a molecule differs slightly from the
external field then the exact resonance frequency is the characteristic of the chemical
environment of the nucleus (CHEMICAL SHIFT)

The magnetic nuclear spins in a sample are detected through their FID. The FID is induced by:
i) Allowing magnetic nuclear spins to reach thermal equilibrium in a large magnetic
field.
ii) Rotating the nuclear spin polarizations by a radiofrequency pulse and
iii) Detecting and amplifying the weak radiofrequency signal that is emitted as the
spins resume their precessional motion in the magnetic field.

In order to explain the behaviour of a nuclear spin during NMR pulse sequences, the vector
model was developed.

 NMR data is obtained by observing the net effect of the nuclei involved. Taking
hydrogen (proton) as an example, it has spin ½ and considering a collection of similar
spin ½ nuclei in the applied field means they will occupy two possible orientations
relative to the applied static magnetic field, B0 (Figure 1.0). The two states are mI = +½
which is a lower energy, more stable state () and mI = -½, which is the upper energy
state ().

½
E
B0

½
Figure 1. 1: Two possible orientations ( and ) that a spin ½ nuclei can take in the applied static field.

 Two allowed transitions which are (a)  ; absorption of energy and (b)  ;
induced emission.
 At thermal equilibrium, the Boltzmann distribution of energies (equation 1.6) is
maintained and there will be excess of nuclei in the  state hence an NMR signal;

N −∆𝐸/𝐾𝑇
=𝑒
N

= 1- h/kT

WHAT HAPPENS AFTER THE SAMPLE IS PUT IN A MAGNET

Magnetization vector

z z

M0

x y
x y

Figure 1. 2: Representation of like spins by a net magnetization vector

 Magnetization that is put into the x,y plane will precess at the Larmor frequency of each
spin. This precession, the FID, is detected by a coil wound along the x or y-axis.
 The concept of the rotating frame is employed, wherein the axes are defined as rotating at
the Larmor frequencies. Thus in the rotating frame, a magnetic moment vector precessing
at the Larmor frequency will appear to be motionless.
Figure 1. 3: Net magnetization at equilibrium

Magnetization

Observable signal

x
y

Figure 1. 4: Projection of magnetization onto the transverse plane

RELAXATION IN NMR SPECTROSCOPY

There are two types of relaxation: longitudinal or spin-lattice (T1) and transverse or spin-spin
(T2).
 T1 is the measure of how fast the magnetization relaxes back along the z-axis and
corresponds to the process of establishing (or re-establishing) the normal Gaussian
population distribution of  and  spin states in the magnetic field.
 T2 is the measure of how fast the spins exchange energy in the x,y (transverse) plane thus
corresponds to loss of phase coherence among nuclei.
Return of magnetization to the z-axis inherently causes loss of magnetization in the x-y plane
and as such T2 relaxation tends to be equal or faster than T1 relaxation and therefore the line
width of an NMR signal is determined by T2 (short T2 gives broader lines) and the maximum
repetition rate during acquisition of an NMR signal is determined by T1 (short T1 means signal
can be acquired faster). An understanding of relaxation processes is important for the proper
measurement and interpretation of NMR spectra because of the following considerations.

1. The very small energy difference between  and  states of a nuclear spin orientation in a
magnetic field results in a very small excess population of nuclei in the ground than the
excited states. For many nuclei relaxation (i.e., return from excited to ground state) is a
very slow process, with half-lives on the order of 0.1 to 100 seconds for a spin ½ nucleus
compared to micro-, pico- and femtoseconds for relaxation of electronic and vibrational
transitions.
2. NMR lines are extraordinarily sharp, and extraordinarily close together (in energetic
terms) compared to other spectroscopic methods. So much so that Heisenberg
Uncertainty Broadening (which is a function of lifetime of a given energy state, and
hence relaxation rates) is a dominant feature of many NMR spectra, and can limit our
ability to measure and interpret spectra. When relaxation is very fast, NMR lines
becomes broad therefore J-couplings may not be resolved or the signal may even be
difficult or impossible to detect leading to wrong assignment of spectra.

3. The success of many multipulse experiments, especially 2D and 3D spectra, depends

 There are many factors that affect the T1 and T2 relaxation times and they include the
nature and the rate of the internal molecular motions among others.
 Molecular motions that occur at a rate comparable to the resonance frequency, , for the
nucleus are most effective in promoting spin-lattice relaxation, i.e., yield the lowest
values for T1. T2 values can be decreased even further as the molecular motion becomes
 slower than , but T1 values will begin to increase. These relationships can be expressed
generally as follows:

T1

Log(Tn)

T2
Intermediate
Slow motion motion Fast motion

Log(c-1)

Figure 1. 3: A schematic illustration of the dependence of T1 and T2 on molecular tumbling rates, c. c is the
molecular correlation time or the time it takes the average molecule to rotate one radian.