NUCLEAR MAGNETIC RESONANCE

NUCLEAR SPIN

The nuclei of some atoms have a property called SPIN.

These nuclei behave as if
they were spinning.
.. we dont know if they actually do spin!

This is like the spin property

of an electron, which can have
two spins: +1/2 and -1/2 .
Each spin-active nucleus has a number of spins defined by
its spin quantum number, I.
The spin quantum numbers of some common nuclei follow ..

Spin Quantum Numbers of Some Common Nuclei

The most abundant isotopes of C and O do not have spin.

Element
Nuclear Spin
Quantum No

12

13

1/2

1/2

14

16

17

19

5/2

1/2

(I)
No. of Spin
States

Elements with either odd mass or odd atomic number

have the property of nuclear spin.
The number of spin states is 2I + 1,
where I is the spin quantum number.

THE PROTON
Although interest is increasing in other nuclei,
particulary C-13, the hydrogen nucleus (proton)
is studied most frequently, and we will devote
our attention to it first.

NUCLEAR SPIN STATES - HYDROGEN NUCLEUS

The spin of the positively
charged nucleus generates

a magnetic moment vector,

+ 1/2

- 1/2
TWO SPIN STATES

The two states

are equivalent
in energy in the
absence of a
magnetic or an
electric field.

THE RESONANCE PHENOMENON

absorption of energy by the
spinning nucleus

Nuclear Spin Energy

Levels
N

-1/2
unaligned

In a strong magnetic
field (Bo) the two
spin states differ in
energy.

+1/2

Bo

aligned

Absorption of Energy
quantized
Opposed

-1/2

-1/2

E
E = h

Radiofrequency

+1/2
Applied
Field

Bo

Aligned

+1/2

THE ENERGY SEPARATION DEPENDS ON Bo

- 1/2

= kBo = h

degenerate
at Bo = 0

+ 1/2
Bo

increasing magnetic field strength

The Larmor Equation!!!

E = kBo = h

can be transformed into

gyromagnetic

frequency of
the incoming
radiation that
will cause a
transition

B0

ratio

Bo
strength of the
magnetic field

is a constant which is different for

each atomic nucleus (H, C, N, etc)

A SECOND EFFECT OF A STRONG MAGNETIC FIELD

WHEN A SPIN-ACTIVE HYDROGEN ATOM IS

PLACED IN A STRONG MAGNETIC FIELD
.. IT BEGINS TO PRECESS

OPERATION OF AN NMR SPECTROMETER DEPENDS

ON THIS RESULT

Nuclei precess at

frequency when
placed in a strong
magnetic field.

RADIOFREQUENCY
40 - 600 MHz

h
If = then
energy will be
absorbed and
the spin will
invert.

NUCLEAR
MAGNETIC
RESONANCE
NMR
S

Resonance Frequencies of Selected Nuclei

Isotope Abundance

(radians/Tesla)

Bo (Tesla)

Frequency(MHz)

99.98%

1.00
1.41
2.35
7.05

0.0156%

1.00
7.05

6.5
45.8

41.14:1

1.108%

1.00
2.35
7.05

10.7
25.0
75.0

67.28

1.00

40.0

13

19

100.0%

42.6
60.0
100.0
300.0

267.53

251.7

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

For a net positive signal

there must be an excess
of spins in the lower state.

induced
emission

excess
population

Saturation = equal populations = no signal

CLASSICAL INSTRUMENTATION
typical before 1960
field is scanned

A Simplified 60 MHz
NMR Spectrometer
RF (60 MHz)
Oscillator

Transmitter

absorption
signal

RF
Detector

Recorder

Receiver

MAGNET

MAGNET

Probe

~ 1.41 Tesla
(+/-) a few ppm

Fortunately, different types of protons precess at

different rates in the same magnetic field.
Bo = 1.41 Tesla

N
EXAMPLE:

59.999995 MHz

59.999700 MHz

O
CH2 C CH3

h
60 MHz

59.999820 MHz

S
Differences are very small,
in the parts per million range.

To cause absorption
of the incoming 60 MHz
the magnetic field strength,
Bo , must be increased to
a different value for each
type of proton.

IN THE CLASSICAL NMR EXPERIMENT THE INSTRUMENT

SCANS FROM LOW FIELD TO HIGH FIELD
LOW
FIELD

HIGH
FIELD
NMR CHART

as
e
r
inc

DOWNFIELD

Bo
g
in

UPFIELD
scan

NMR Spectrum of Phenylacetone

O
CH2 C CH3

NOTICE THAT EACH DIFFERENT TYPE OF PROTON COMES

AT A DIFFERENT PLACE - YOU CAN TELL HOW MANY
DIFFERENT TYPES OF HYDROGEN THERE ARE

MODERN INSTRUMENTATION
PULSED FOURIER TRANSFORM
TECHNOLOGY
FT-NMR
requires a computer

PULSED EXCITATION
N

1
BROADBAND
RF PULSE
contains a range
of frequencies

1 ..... n

2
O
CH2 C CH3

S
All types of hydrogen are excited
simultaneously with the single RF pulse.

FREE INDUCTION DECAY (FID)

( relaxation )

1
O

CH2 C CH3

3
1, 2, 3 have different half lifes

COMPOSITE FID
time domain spectrum

1 + 2 + 3 + ......
time

FOURIER TRANSFORM
A mathematical technique that resolves a complex
FID signal into the individual frequencies that add
together to make it. ( Details not given here. )
TIME DOMAIN

converted to

FID

COMPLEX
SIGNAL

FREQUENCY DOMAIN
NMR SPECTRUM

FT-NMR
computer
Fourier
Transform

a mixture of frequencies
decaying (with time)

DOMAINS ARE
MATHEMATICAL
TERMS

1 + 2 + 3 + ......
individual
frequencies
converted to a spectrum

The Composite FID is Transformed

into a classical NMR Spectrum :

O
CH2 C CH3

frequency domain spectrum

COMPARISON OF
CW AND FT TECHNIQUES

CONTINUOUS WAVE (CW) METHOD

THE OLDER, CLASSICAL METHOD

The magnetic field is scanned from a low field

strength to a higher field strength while a constant
beam of radiofrequency (continuous wave) is
supplied at a fixed frequency (say 100 MHz).
Using this method, it requires several minutes to plot
an NMR spectrum.
SLOW, HIGH NOISE LEVEL

PULSED FOURIER TRANSFORM

(FT) METHOD
FAST
THE NEWER COMPUTER-BASED METHOD

LOW NOISE

Most protons relax (decay) from their excited states

very quickly (within a second).
The excitation pulse, the data collection (FID), and
the computer-driven Fourier Transform (FT) take
only a few seconds.
The pulse and data collection cycles may be repeated
every few seconds.
Many repetitions can be performed in a
very short time, leading to improved signal ..

IMPROVED SIGNAL-TO-NOISE RATIO

By adding the signals from many pulses together, the
signal strength may be increased above the noise level.

noise

signal

enhanced
signal

1st pulse
2nd pulse

nth pulse

add many
pulses
etc.

noise is random
and cancels out