Lecture 7

Introduction to Nuclear Magnetic

Resonance Spectroscopy (NMR)
(Part 1)
 NMR Spectrometers with
Superconducting Magnets

❖ Until recently all NMR spectrometers were very large and

expensive instruments.
Internal Structural Components of an NMR Spectrometer
 NMR Spectrometers with
Permanent Magnets

❖ Recent developments in NMR technology have resulted in smaller

and cheaper bench top units.
Influence of a Strong External Magnetic Field

➢Normally, nuclei do not take ➢ However, in the presence of

on a specific orientation. a strong magnetic field some
nuclei align along the axis of
the magnetic field and
“precess” like a spinning top.
 Math of Nuclei Spinning
➢ Allnuclei carry a charge.
➢ This charge can “spin” on the nuclear axis.
➢ The result of this circulation is a magnetic dipole along the
axis.

➢ The total angular momentum of this spinning charge can be

described in terms of a nuclei’s quantum spin number (I).

➢The magnitude of I depends on its mass number (# of protons +

neutrons) and its atomic number (# of protons).

Mass # Atomic # I
Odd Even or Odd 1/2, 3/2, 5/2, …
Even Even 0
Even Odd 1, 2, 3, …
NMR Periodic Table
 Magnetic Properties of Some Important Nuclei
Isotope Spin Natural Quadrupole moment Gyromagnetic ratio Relative Relative NMR frequency
Abundance Q (10-28m2)  (10-7 rad s-1T-1) sensitivity sensitivity (MHz) at a field
to 1H times natural (T) of 2.3488
abundance
1H 1/2 99.98 - 26.7522 1.00 1.00 100.000
2H 1 1.5 x 10-2 2.87 x 10-3 4.1066 9.65 x 10-3 1.45 x 10-6 15.351
7Li 3/2 92.58 -3.7 x 10-2 10.3976 0.29 0.27 38.863
11B 3/2 80.42 4.1 x 10-2 8.5847 0.17 0.13 32.084
13C 1/2 1.108 - 6.7283 1.59 x 10-2 1.76 x 10-4 25.144
14N 1 99.63 1.67 x 10-2 1.9338 1.01 x 10-3 1.01 x 10-3 7.224
15N 1/2 0.37 - -2.7126 1.04 x 10-3 3.85 x 10-6 10.133
19F 1/2 100 - 25.1815 0.83 0.83 94.077
23Na 3/2 100 0.10 7.0704 9.25 x 10-2 9.25 x 10-2 26.451
25Mg 5/2 10.13 0.22 -1.6389 2.67 x 10-3 2.71 x 10-4 6.1195
31P 1/2 100 - 10.8394 6.63 x 10-2 6.62 x 10-2 40.481
35Cl 3/2 75.53 -8.2 x 10-2 2.6242 4.70 x 10-3 3.55 x 10-3 9.798
39K 3/2 93.1 5.5 x 10-2 1.2499 5.08 x 10-4 4.73 x 10-4 4.667
51V 7/2 99.76 2.17 x 10-3 -5.2 x 10-2 0.38 0.38 26.289
75As 3/2 100 0.29 4.5961 2.51 x 10-2 2.51 x 10-2 17.126
77Se 1/2 7.58 - 5.1214 6.93 x 10-3 5.25 x 10-4 19.067
113Cd 1/2 12.26 - -5.9609 1.09 x 10-3 1.33 x 10-3 22.182
 Solvents in NMR
❖Most NMR experiments are carried out in solution.
➢ Deuterated Solvents are used in NMR such as
D2O (Deuterated Water)
CDCl3 (Deuterated Chloroform) etc…

Deuterated Solvents are used for two reasons:

1) Deuterium does not show up in the 1H NMR spectrum so it
does not complicate the spectrum or hide peaks, BUT it
does appears in the carbon spectra.
2) The Deuterium in the solvent acts as a “lock”.
➢ The NMR instrument locks onto the known solvent
frequency AND uses it as a reference.
➢ This allows the NMR to adjust for changes in the
magnetic field during the experiment, so that the
experimental conditions stay constant.
 Nuclear Magnetic Moment ()

❖ The magnitude of a nuclei’s magnetic dipole is given by its

nuclear magnetic moment ():

 = I
➢  is the nuclear magnetic moment.
➢  is magnetogyric (gyromagnetic) ratio.
➢ I is the nuclear spin.
➢ ħ is the reduced Planck’s constant (1.054589x10-34 Js)
Orientation of Nuclei in an External Magnetic Field

➢ In an external magnetic field a nucleus with spin I has 2I

+ 1 possible orientations.
➢These are given by the magnetic quantum number MI
which has values of -I, -I+1, -I + 2, …, I.
➢ So for a nucleus with I = 5/2 there are 6 possible
orientations in an external field with the MI values of (–5/2,
-3/2, -1/2, 1/2, 3/2 and 5/2).

Most of the most commonly used nuclei in NMR

spectroscopy have I = ½ (1H, 13C and 15N).
Orientation of Nuclei in an External Magnetic Field

➢ Nuclei with I = 1/2 have two

possible energy levels in an external
magnetic field.
➢ Some nuclei align with the
magnetic field (low energy state)
while others align in the opposite
direction (high energy state).

Bo ➢ On average slightly more nuclei

align with the magnetic field (low
energy) state.

Note: Bo is the externally applied magnetic field.

Orientation of Nuclei in an External Magnetic Field

➢ Nuclei with I = 1/2 have two possible energy levels in an

external magnetic field.

 = −
E E
 = 

B0
➢ The energy difference between energy levels is given by the
equation:
E = B0
 A More Complicated Explanation

➢ The nuclei are not statically aligned

parallel or antiparallel to Bo.
➢ Instead they remain at a certain
fixed angle with respect to Bo and
“precess” like a top around the z
axis of Bo.
➢ The frequency of this precession is
called the Larmor frequency and
is given by the formula:

γB0
=
2π
 Excitation in NMR Spectroscopy

➢ There are two allowed transitions (I = ± 1).

➢ Both are equally probable.
 Population of Energy Levels
➢ Assuming that I = 1/2, then the population of the two energy
states  and  will be governed by the Boltzmann distribution:
N − E kT −B0 kT hv
=e =e = 1−
N kT
➢ As h < kT there is a slight excess (~ 1 x 10-5) of the
population of the +1/2 or  state and a bulk magnetization
M along the z axis:

 state

 state
 Effect of RF Irradiation

Equilibrium State Radio frequency

pulse causes bulk
magnetization to flip
into the xy plane.
Relaxation After Excitation

Hypothetical Situation:
The nuclei resonate forever.

Reality:
The nuclei return to
equilibrium and the signal in
the XY plane decays. This
process is called relaxation.
The resulting signal is called a
free induction decay (FID).
 Relaxation Mechanisms
❖ There are two main types of relaxation in NMR spectroscopy.
➢ Longitudinal (spin-lattice) relaxation (T1)
➢ Transverse (spin-spin) relaxation (T2)

❖ In longitudinal relaxation energy is transferred from the excited

nuclei to the lattice resulting in the excited nuclei returning to its
lower energy state.
➢ This is the process by which the z magnetization reappears
after a RF pulse.
❖ In transverse relaxation a nucleus of one atom transfers its
energy to another atom in a low-energy state.
➢ The result is a “blurring” of the bulk magnetization vector in the
xy plane causing the observed NMR signal to decay.
 Obtaining an NMR Spectrum
❖ Most samples have more then one type of magnetically
equivalent sets of nuclei and thus multiple Larmor frequencies.

❖ Two methods exist for achieving resonant conditions in NMR

spectroscopy.
➢ CW (continuous wave) NMR spectroscopy.
➢ FT (Fourier transform) NMR spectroscopy.

❖ In CW resonance conditions are met by sweeping the Bo

field bringing the larmor frequencies into resonance one at a
time.

❖ In FT-NMR a short powerful RF-pulse is used to excite all of

the groups of nuclei at the same time.
 Processing the signal

Fourier Transform

❖ The FID must be processed by Fourier transformation to obtain

the frequency domain information of a normal spectrum from the
time domain of the FID.
What Does a 1H NMR Spectrum Look Like?

a
CH3 CH2 O CH2 CH3
a b b a b

➢ A NMR spectrum is a plot of signal intensity (Y axis)

against chemical shift (X axis).