Nuclear Magnetic Resonance

(NMR)






Basic Principles
NMR- What is it good for ?
The Nuclear Magnetic Moment
All atomic nuclei can be characterized
by a nuclear spin quantum number, I. I
can be 0 and any multiple of .

Nuclei with I= 0 do not possess
nuclear spin and consequently are
termed NMR silent or NMR inactive.

All nuclei with I0 possess spin,
charge, and angular momentum L,
resulting in a nuclear magnetic
moment . = L
Where is the magnetogyric ratio of
the nucleus.


I = the nuclear spin quantum number

For Nuclei of: I Example

Odd Mass Half Integer
1
H,
13
C

Even Mass/Even Charge Zero
12
C,
16
O

Even Mass/Odd Charge Integer
2
H,
14
N


I f I = 0, NMR I nactive

If I 1, Quadrupolar (non-spherical nuclear charge
distribution)
Magnetic Quantum Numbers

I is quantized producing (2I+ 1) discrete values of angular
momentum, m
I
m
I
= I, I -1, -I
The magnetic moment
The z-component of the magnetic moment is

The energy of a magnetic moment of a nuclear
spin in a magnetic field is

To conduct an NMR expt we need to put the
sample in an external static magnetic field. By
convention the direction of this field is along the
z-axis and is represented by the magnitude B
0,
then



L =
z z z
m L = =
0
B E
z

=
0
0
0 0
B
B E
B m B E
z z
e
e

=
= = A
= =

(m
z
=1/2 and -1/2)
t

v
2
0
B
=
-ve sign ?
The direction of precession is left handed as
compared to the direction of B
0
The Larmor Frequency
A nuclear magnetic moment will precess about the axis of an
externally applied field at a frequency proportional to the strength
of the applied field, Bo.
= Bo(rad/s)
= Bo/2 LarmorFrequency
The direction of motion can be clockwise or counterclockwise and
is determined by the sign of . By convention, the field is applied
along the z axis of a Cartesian co-ordinate frame.
Magnetic Properties of Selected Nuclei

Nucle
us
Abund
ance %
Spin
, I

(/10
7
Ts)
1H

99.98 26.75
2H(D
)
0.02 1 4.10
13C 1.1 1/2 6.73
14N 99.64 1 1.93
15N 0.365 1/2 6.73
19F 100 1/2 25.1665
35P 100 1/2 10.8289
35Cl 75.4 3/2 2.621
37Cl 24.6 3/2 2.1718
degenerate
at B
o
= 0
AE
= kB
o
= hv
+ 1/2
- 1/2
increasing magnetic field strength
B
o
Large collection of spins placed in a
magnetic field.
Bulk magnetic moment ---vector sum of the
microscopic magnetic moments in the bulk
of the material

=
n
i
i
M

Randomly oriented magnetic moments

A net magnetic moment M
0
appears, aligned
with the external magnetic field and the spin
system is said to be at equilibrium.
POPULATION AND SIGNAL STRENGTH
The strength of the NMR signal depends on the
population difference of the two spin states
Radiation induces both
upward and downward
transitions.
resonance
induced
emission
excess
population
For a net positive signal
there must be an excess
of spins in the lower state.
Saturation = equal populations = no signal
The selection rule for magnetic resonance is

Other transitions are forbidden.


1 = A
I
m
The energy difference is very small compared to kT
rad/T.S
rad/T.S
Resonance Frequencies of Selected Nuclei
Isotope Abundance B
o
(Tesla) Frequency(MHz) (radians/Tesla.S)
x10
6


1
H 99.98% 1.00 42.6 267.53
1.41 60.0
2.35 100.0
7.05 300.0

2
H 0.0156% 1.00 6.5 41.1
7.05 45.8

13
C 1.108% 1.00 10.7 67.28
2.35 25.0
7.05 75.0

19
F 100.0% 1.00 40.0 251.7
4:1
4:1
A Simplified 60 MHz
NMR Spectrometer
hv
Probe
N
RF
Detector
Recorder
RF (60 MHz)
Oscillator
~ 1.41 Tesla
(+/-) a few ppm
absorption
signal
MAGNET
MAGNET
S
N
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