Nuclear Magnetic Resonance

N. Chandrakumar

Zeeman Hamiltonian
The magnetic moment
r
associated with a spin is given by:
= I
r
r
h

Here, is the magnetogyric ratio and I
r
, the (dimensionless) spin
angular momentum operator. The energy of interaction of a spin with a static
(dc) magnetic field (Zeeman field) is then given by the following relation:
= = H B I B
r r r
r
h

It is the convention to adopt the direction of the magnetic field as the
z-axis, B
0
being its intensity. With this choice of co-ordinate system, we
have:
0
0
z
I
B I
E B m

=
=
H h
h

The result is a set of (2I+1) energy levels that are equally spaced, the
spacing being hB
0
.
Dynamically, the spin magnetic moments precess about the magnetic
field, the magnitude of the torque being the derivative wrt orientation angle
of the energy of the magnetic moment in the magnetic field, equal in turn to
the rate of change of angular momentum:
d
dt
d
dt

=
=
I
C B

B
r
r
r
h
r
r
r

This vector equation may be solved as a set of coupled differential equations
in the components of the magnetic moment. Because B
r
represents a static
(dc) magnetic field, one finds that the z-component of magnetic moment is
independent of time, while the x- and y-components oscillate in time with
the angular frequency
0
= B
0
, which is the so-called Larmor precession
frequency and also represents the energy level difference in units of angular
frequency.
NMR Spectroscopy

NMR Spectroscopy involves the interaction of nuclear magnetic
moments with the magnetic component of resonant electromagnetic
radiation, the experiment being carried out with the sample placed in a
Zeeman magnetic field, in which nuclear spins (magnetic moments)
precess at a characteristic Larmor frequency.
NMR transitions are magnetic dipole transitions, and obey a selection
rule for the change allowed in the magnetic quantum number m (component
of spin angular momentum in the direction of the Zeeman field):

m =1

The frequency of an NMR transition is governed by:
( )
0
0 0
E B
B

=
=
h

The transition frequency is governed by the intensity of the Zeeman field, as
well as the magnetogyric ratio of the spins, a characteristic of the nuclear
isotope in question. It turns out however that the magnetic field sensed at the
nucleus is modified by the local environment, primarily the electron density
around the nucleus in question and in its neighborhood:
( ) ( )
0 0
1 B =

Here, is a screening (or shielding constant), that describes the effect of
the surrounding electron density including neighbouring groups and also
electron circulation in aromatic rings in modifying the field intensity at the
site of the nucleus.
In addition, the NMR resonance frequency is modified by
internuclear, through-bond scalar spin-spin coupling J, which relates to the
functional groups in the neighborhood of the probe nuclear spin.
Taking both these effects into account, the resonance frequency of the
ith nuclear spin may therefore be given by:
( )
0
1
2
i
i i ij j
j
B J m

= +

Bloch Equations

The magnetization of an ensemble of non-interacting spins with spin
quantum number I (eg. atomic nuclei in a molecule, or unpaired electrons in
molecules or free radicals), when they are immersed in a magnetic induction
(or magnetic field of intensity) B
0
along the z direction is given by the Curie
susceptibility:
0 0 0
M B =

Here the Curie susceptibility
0
is given by:
( )
2 2
1
0 3
N I I
kT

+
=
h


N is the number of spins per unit volume; is the magnetogyric ratio (a
property of the spin) and T the absolute temperature.
This corresponds to a state of thermal equilibrium governed by the
Boltzmann distribution of spin populations among the (2I+1) allowed energy
levels of the spin system, the ratio of populations of two energy levels being
given by:
( )
( )
exp
i j
E E
i
kT
j
N
N

=

In thermal equilibrium, the magnetization of the ensemble is parallel to the
direction of the magnetic field, while components of magnetization
transverse (perpendicular) to B
0
vanish.
Dynamically, the spins precess around B
0
with the Larmor frequency:
0 0
B =

This corresponds to the fact that the energy difference between successive
energy levels of the (2I+1) level system is h
0
.
The Bloch equations are phenomenological equations that describe the
return of the spin magnetization components to their equilibrium values
following the creation of a non-equilibrium condition by suitable means.
( )
0
1
2
2
z
z
x x
y y
M M
dM
dt T
dM M
dt T
dM M
dt T

=
=
=

Clearly, the Bloch equations imply that the return to equilibrium is governed
in general by two first order rate constants, T
2
1
pertaining to the transverse
components and T
1
1
to the longitudinal component of magnetization. The
former is known as the transverse or spin-spin relaxation rate, while the
latter is the longitudinal or spin-lattice relaxation rate.
Relaxation corresponds to radiationless transitions of the spin system,
that occur, for example, in readjusting energy level populations to their
equilibrium values. Energy conservation requires that the energy released
when a radiationless transition occurs from a higher to a lower energy level
be soaked up by the other degrees of freedom of the system in which the
spins are embedded (eg. molecules in liquid, solid or gaseous phase). This
would require that there exist such a motional mode of the system that can
accept the quantum of energy released. Accordingly, the efficiency of
longitudinal relaxation is governed by the spectral density (ie, energy
available in motions) at the Larmor frequency and at double the Larmor
frequency. Measurement of T
1
can therefore throw considerable light on
molecular motions.
It may be noted that transverse relaxation is governed in addition by
the spectral density at zero frequency. The exponential time decay of non-
zero transverse magnetization implied by the Bloch equations leads to the
Lorentzian lineshape of magnetic resonance signals in solution state, where
the approximation of non-interacting spins is often reasonable. In this
situation, the relation between the full linewidth at half maximum height
(
1/2
) and the relaxation rate, T
2
1
, is given by:
1
2
2
1
T

=

In the solid state on the other hand, lineshapes are often Gaussian.
Lineshapes that are intermediate to these two extremes are also often
encountered in magnetic resonance spectra, and are termed the Voigt
lineshape.