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1 2

Nucleus:

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Electromagnetic radiation absorption or excitation of nucleus:

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11 12
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13 14

15 16
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Nuclear orientation and precession:

Precessional orbit

Bo x

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Flip

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Spin-flip
Excitation and relaxation

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Nuclear relaxation:

 Relaxation is the process by which the spins in the

sample come to equilibrium with the surroundings.
 The rate of relaxation determines how fast an
experiment can be repeated.
 The rate of relaxation is influenced by the physical
properties of the molecule and the sample.
 An understanding of relaxation processes is important
for the proper measurement and interpretation of NMR
spectra.

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Excitation and relaxation of nucleus

To examine an element by NMR,

Number of spin quantum I> 0
magnetic moment µ≠0

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Precession

Magnetic properties of the nuclei:

 It is necessary to assume:
nuclei rotate about an axis and thus have the
property of spin.

 Furthermore, it is necessary to postulate that the angular

momentum associated with the spin is a half-integral multiple of h/2p
(h=Planck’s constant). The maximum spin component for a
particular nucleus is its spin quantum number, I.
I = half-integral values 0, ½, 1, 3/2, ……..9/2 depending
on the particular nucleus.
 It is found that a nucleus will have (2I+1) discrete states. The
component of angular momentum for these states in any chosen
direction will have values –I, (-I+1), …..(I-1), I.
 Nuclear spin angular momentum is a quantized property of nucleus
in each atom, it is assigned based on the property of neutrons and
protons.

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 Nuclei in the lower energy state can be ‘spin-flipped’ into

Nuclear Spin
 A nucleus with an odd atomic number or an odd
mass (neutron) has a nuclear spin. Nuclei of such
are 1H, 13C, 15N, 19F, 31P etc.
 The spinning charged nucleus generates a magnetic
field.
their higher energy state by the supplying of radio frequency
energy.
 A precise amount of energy needs to be supplied, or this
excitation to a higher energy state will not occur.
 The amount of energy required can be supplied by the
absorption of radio waves.

 The frequency of the radio waves required to produce the

‘spin-flip’ is termed the resonance frequency.

External magnetic filed

Bo

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 When an electromagnetic radiation beam is equal to the energy difference (E=

h.) applied to a sample containing “H” and placed in the “Bo" magnetic field, it is
absorbed by protons at low energy level and protons increases to the high
energy level that it opposes to the magnetic field (magnetic resonance = nuclear
transition).

 A proton, which has increased to a high energy level, returns to the basic state by
giving back the energy that it absorbs after a period of time (0.1  1 sec).
relaxation = relaxation).

Fli
E= h. =.Bo/I
p  =.Bo/2p

Ho = applied magnetic field strength

 = the frequency of absorbed energy
= magnetic moment (constant, = .h.I / 2 )
= gyromagnetic constant; different for each element there
I = spin quantum number (fixed)
h= Planck constant (6.624 x 10-27 erg.sn)

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 Resonance: In NMR spectroscopy, resonance is
the absorption of energy by a precessing nucleus
and the resulting “flip” of its nuclear from a lower
energy state to a higher energy state.
 The precessing spins induce an oscillating
magnetic field that is recorded as a signal by the
instrument.
 Generally, the precession is a quantized
phenomenon.
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 If the ordered nuclei are subjected to EM radiation of the proper
frequency the nuclei aligned with the field will absorb energy and
"spin-flip" to align themselves against the field, at higher energy
state. When this spin-flip occurs the nuclei are said to be in
"resonance" with the field, hence the name for the
technique, Nuclear Magentic Resonance or NMR.
 The amount of energy, and hence the exact frequency of EM
radiation required for resonance to occur is dependent on both the
strength of the magnetic field applied and the type of the nuclei being
studied. As the strength of the magnetic field increases the energy
difference between the two spin states increases and a higher
frequency (more energy) EM radiation needs to be applied to achieve
a spin-flip (see image below).
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Figure: The nuclear magnetic moment of a spinning

nucleus.

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Q. The NMR
Precessional orbit Event-What
causes “Spin
Flip”?

When the frequency

of radiation exactly
matches the energy
gap between the spin
states, the nucleus
undergoes a “spin
flip”.

Nuclear spin flip:

Change in orientation of the nuclear spin axis upon energy
absorption (excitation) or energy release (relaxation).

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Spinning of Nucleus:
All nuclei carry a charge. In same nuclei charge spins on the
nuclear axis and this circular, charge generates a magnetic dipole
along the axis. The angular momentum of the spinning charge
can be described in terms of quantum number I, “I= 0, ½, 1, 3/2,
2, 5/2………. And so on. If spin I=0 no spin and hence no, NMR
phenomenon.
Spinning
nucleus

Precessional orbit Nuclear magnetic

dipole moment 

Spinning nucleus

Bo

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NMR Spectroscopy:
 Protons and neutrons in a nucleus behave as if they are Nuclear Spin: Structure of Proton and Neutron:
spinning. The spinning charge in the nucleus creates a
magnetic moment ().
 Protons and neutrons are fermions and have spin I= ½.
 How can a neutron, which has no charge, exhibit a
magnetic moment?
 Protons and neutrons form pairs of opposite total angular
momentum in atomic nuclei.
 Thus, the magnetic moment of a nucleus with an even
number of both protons and neutrons is zero.
 All isotopes that contain and odd number of protons and/or
neutron have an intrinsic magnetic moment and angular
momentum; in other words, a non-zero nuclear spin.

Proton Neutron

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Structure of Nucleus and Nuclear Spin and Nuclear Magnetic moments

N +
N Charged particles The Spin Quantum Number (ms) describes the
S ↓
Motion → spin angular momentum of a nucleus. A nucleus
S
→ spin spins around an axis and has both angular
↓ momentum and orbital angular momentum.
magnetic field
Nuclear magnetic moment Because angular momentum is a vector, the
Spin Quantum Number (s) has both a
magnitude (1/2) and direction (+ or -).

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Table:
The NMR Behavior of Magnetic: Q. Which of the following nuclei are no NMR active and why?
Some Common Nuclei
o All nuclei with odd 1H, 2H, 3H, 12C, 13C, 16O, 17O, 18O, 14N, 15N, 19F, 12S, 12C, 31P, 56Fe.

Magnetic Non magnetic number of protons

nuclei nuclei
o All nuclei with odd Energy
absorption
Energy
release
1H 12C
number of neutrons (Excitation) (relaxation)
13C 16O
Flip of
nucleus
2H 18O
Nonmagnetic:
14N 32S
o Nuclei with even number
19F 54Fe
of both protons and
31P 58Fe neutrons

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Charge distributions:

Figure: Charge distribution is spherical and non-spherical nuclei

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Charge distributions:

Figure: Charge distributions in a spin-1/2 nucleus and in a

quadrupolar nucleus. A spin-1/2 nucleus has a spherical
distribution of charge. A quadrupolar nucleus has an asymmetric
distribution of nucleons, producing a non-spherical positive
charge distribution. The nuclear charge distribution (black
charges) interacts asymmetrically with electric field gradients
(blue charges) in a molecule.

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Spinning of Proton/Neutron Single Proton/Neutron: =Bo = /2p  = Resonance frequency or

Larmour frequency
Z  = gyromagnetic ratio
B0= magnetic field strength
Nuclear
magnetic
There are electric Precession
 moment The proton also
charge on the surface  has mass which
of the proton, thus J generates an
creating a small Angular angular
current loop and momentum
momentum J
generating magnetic when it is
moment  .
spinning
Applied
magnetic 
field Spinning
Bo
nucleus

Thus proton “magnet” differs from the conventional magnetic bar in that it
also possesses angular momentum caused by spinning.

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Precession

Nuclear Nuclear
magnetic magnetic
moment moment

Spinning Spinning
nucleus
nucleus

Precession

Figure: Classical representation of a proton

precessing in a magnetic field of magnitude
Bo in analogy with a precessing spinning top.

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This unique value of ‘γ’ for each Field Spin=1/2

element’s nucleus different from
every other element is what makes
These tiny
+1/2
multi nuclear NMR possible -1/2 Energy
nuclear magnetic
Magnetic moments are Nuclear Spin
moment similar to the bar
Magnetic +1/2
moment -1/2
SPIN magnets which
SPIN are influenced by
Externally applied
magnetic fields
Spin Quantum
number value= 3/2 Illustration is
a case of
or SPIN=3/2
results in 4
The central nucleus of equally
or spaced
The value of γ some of the elements posses intrinsic spin energy
differs from one and hence also can be or
levels
nucleus to the other.
associated with a
Only Discrete
magnetic moment
2π ν = γ H Similar effects are possible with electrons
orientations of
the spin are
also but only in PARAMGNETIC IONS or possible due
Molecules when there are unpaired electrons Applied
to the
present. Here the reference is only to magnetic
Electromagnetic radiation with quantization
Diamagnetic Samples (compounds) to field
frequency ν can cause introduce NMR exclusive of any other criteria at
transition between these levels effects. Discrete orientations atomic
and this is the resonance RESULTS in discrete regimes
phenomenon energy levels

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Periodic table for NMR active and inactive nuclei

I =1/2

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Periodic table of Isotopes:

Nuclear spin quantum number (I)

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