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Chapter 2

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Chapter 2

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Nesrine Chergui
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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‫بسم الله الرحمن الرحيم‬

Magnetique resonance
imagering

Created bay :

Iles Amel
CHAPTER 2

Spin Physics
INTRODUCTION

The nucleus (noyau) reacts when immersed in a magnetic field created by a magnet.
For some atomic nuclei (noyaux), such as carbon or oxygen, nothing changes.

Carbon: 6 protons and 6 neutrons Oxygen: 8 protons and 8 neutrons


Other nuclei,
such as the hydrogen atom: It reacts to radiofrequency waves.
An odd number of particles.

Hydrogen atom
Nuclei and spins

• The nucleus is the central core of an atom


and is made up of protons and neutrons.

microscopic magnetization 𝜇 ⃑ which is called spin.


Atomic nuclei spin on themselves; this causes a

• The Nuclear Spin is different from the


electron spin. it acts as if it is a single entity
which has intrinsic angular momentum. It is
represented by symbol, I.
(a) atomic nucleus, (b) Nuclear spin

In the atom , where Z is the atomic number and A is the atomic mass number. The
nuclear spin depends on the mass number, if the mass number is odd then the
nucleus has half-integer spin (1/2I) like the electron while if the nucleus has even
mass number then its spin will be integer spin (I).
• Only nuclei with spin quantum number 𝐼 ≠ 0 can emit or absorb electromagnetic waves. Atomic nuclei
with an odd number of protons, neutrons or both will have an intrinsic nuclear spin.

• The figure shows the example of the helium atom, made up of two protons and two neutrons. It is
electrically neutral.

Electron spin (2 electrons: 1/2 +1/2) = 1,

proton spin (2 protons: 1/2 +1/2) = 1

and neutron spin (2 neutrons: 1/2 +1/2)=1.

Nuclear spin=2

The deterium atom: Nuclear spin=1

= 1 proton and 1 neutron so I=1


NUCLEAR SPIN STATES

The nuclear spin states can take any number, fraction or integer. The number is dependent
on the three points:
1. If both the neutrons and the protons in the nucleus are even in number then the
nucleus has NO spin states (aucun état de spin).
Examples : , , …
2. If the sum of the neutrons and protons in the nucleus is odd then the nucleus has half
integer spin (1/2, 3/2, 5/2, …). , l is the nuclear spin quantum number
Examples: 1H, 13
C, 31
P, 19
F, 15
N, 17
O...
3. If both the neutrons and the protons in the nucleus are odd in number then the nucleus
has an integer spin states (1, 2, 3, …). I=2I+1
Examples: (I=1), (I=1),…
In other words the nucleus with odd number of protons or neutron or both should have the
nuclear spin while if both are even then there is no nuclear spin.
Magnetic quantum number represents spin of the nucleus which has 1 or ½
values as follows:
• a) I =1, for nuclei with even mass number
• b) I =0, for equal number of neutrons and protons due to the tendency of
both these nuclear entity to form pairs in such a way that the individual
spin cancel out. Therefore, 12C and 16O have zero spin and do not
produce NMR signals.
• c) I= 1/2 for nuclei with odd mass numbers. Nuclei of half spin, such as
1H, 13C and 31P are particularly important in NMR, as these are the
nuclei that tend to have the most appropriate NMR characteristics. Some
NMR active nuclei and their properties are listed in Table.
NUCLEAR SPIN TABLE

• The nuclear spin of the various element of the periodic table is shown below. The color code and
their corresponding allowed nuclear spin is shown in the figure. There are certain elements for
which the value of I is unknown.
NUCLEAR SPIN ANGULAR
MOMENTUM
Spin magnetic quantum numbers ms = -1/2, 1/2 (which are also known as spin down
and spin up).

Angular quantum number (m) may have any of


the 2I+1 values, and thus for a nucleus of spin
1/2, m can be +1/2 or -1/2. The two spins are
shown in Figure.

The allowed orientations of the angular


momentum vector of a nucleus of spin 1/2
which is specified by the quantum number (m
=1/2 and -1/2) and describe two cones.
NUCLEAR SPIN QUANTUM
NUMBER
• The nuclear spin quantum number l, determines the allowed
spin states of the nucleus and it is represented by; Allowed:

Spin States = 2l+1,

• In the case of hydrogen, l= 1/2 and hence the allowed spin


states of the nucleus is 2.

• Similarly if the value of l of an element is known we can find


the allowed states of the nucleus of that atom.
• In the absence of an external magnetic field, these orientations
are of equal energy. If a magnetic field is applied, then the
energy levels split. Each level is given a magnetic quantum
number, m.

spin magnetic quantum numbers ms = -1/2, 1/2 (which are also known as spin down
Magnetic Moment of Nucleus

Since the nuclei bear (portent) electrical charge, their spinning produces a magnetic
moment (μ), expressing the strength and direction of the magnetic field surrounding
the nucleus. The field produced by these magnetic dipoles is analogous to those of a
microscopic bar magnets with a north pole and a south pole.
MAGNETIC MOMENT OF
NUCLEUS
• The magnetic moment of the nucleus is closely related to its angular
momentum and its direction is same as that of the angular momentum. The
magnitude of μ is given by µ =ɣ ⃗
⃗ 𝑆 𝑛

Where is the Gyro-magnetic ratio (constant) of the nucleus. Each nuclear


species has a different value of , which is experimentally determined.

the nuclear magnetic moment obeys the same rules of quantization as angular
momentum, the nuclear spin is given by
I (I + 1)

where is the Plank constant: .

µ𝑛 =ɣ h √ ¿ ¿
The result of the magnitude of the nuclear magnetic moment is :
MAGNETIC MOMENT OF
NUCLEUS
• The net or bulk magnetization of the sample is given by M and is the sum
of each individual magnetic vector, or

• since these magnetic moments are vectors and are randomly aligned, the
bulk magnetization arising from the nucleus is zero. There may be
unpaired electrons which give rise to paramagnetic, anti ferromagnetic,
or ferromagnetic properties. However, if an external magnetic field is
applied, the nuclei will align either with or against the field and result in a
non-zero bulk magnetization.
Nuclei in a Static Magnetic
Field B0
NUCLEI IN A STATIC
MAGNETIC FIELD B0
In the absence of magnetic field (Bo) these spins are randomly oriented with respect to each
other; however when subjected to a magnetic field (Bo) the spins align themselves with and
against the direction of Bo corresponding to high and low energy spin states

• B = Bo two possible spin states.


The magnetisation vector is not zero. where n
is the spin number.

The important consequence of nuclear spin is the energy splitting of degenerate Nuclear Spin
states under an external magnetic field. It is possible to drive transition between different spin
states by applying radio-frequency electromagnetic radiation.
NUCLEAR ENERGY LEVELS IN A
MAGNETIC FIELD
In the use of an external magnetic field:
Initially, the nucleus is in the nuclear ground state which is degenerate. The degeneracy of the ground state
is 2I+1. The application of a magnetic field splits the degenerate 2I+1 nuclear energy levels. The energy of a
particular level is

Where B0 is the external magnetic field.


Along the z-direction, which we assume the magnetic field is applied,
by substitution,
NUCLEAR ENERGY LEVELS IN
A MAGNETIC FIELD
A proton with I = 1/2, has two possible orientations either parallel or anti-
parallel with B0, which correspond to low and high energy states.

The green spheres represent atomic nuclei which are either


aligned with (low energy) or against (high energy) the
magnetic field.
NUCLEAR ENERGY LEVELS
As mentioned above, an exact quanta of energy must be used to induce the spin flip or transition.
For any m, there are 2m+1 energy levels. For a spin 1/2 nucleus, there are only two energy levels,
the low energy level occupied by the spins which aligned with B0 and the high energy level
occupied by spins aligned against (contre) B0. Each energy level is given by

where m is the magnetic quantum


number, in this case +/- 1/2. The energy
difference ∆E, between the two states is
proportional to the strength of B0 and is given
by:

Where is Planks constant.

The splitting of the degenerate energy level due to the presence of a magnetic field in
known as Zeeman Splitting
Energy Levels Diagram
ENERGY LEVEL SPIN
DISTRIBUTION
• Application of an external magnetic field creates distinct energy levels
based on the spin angular momentum of the nucleus. Each energy level is
populated by the spins which have the same angular momentum. To
illustrate this, consider a I=1/2 system. There are two energy levels, +1/2
and -1/2, which are populated by spins that have aligned against or with
the external magnetic field, respectively.
The energy separation between these states is
relatively small and the energy from thermal
collisions is sufficient to place many nuclei into higher
energy spin states. The number of nuclei in each spin
state can be described by the Boltzmann distribution.
The Boltzmann equation expresses the relationship
between temperature and the related energy as
shown below.

Where Nupper and Nlower represent the population of Spins configurations


nuclei in upper and lower energy states. according to applied
BOLTZMANN STATISTIC
• At room temperature, the number of spins in the lower energy state, N+,
slightly outnumbers (légèrement plus nombreux que) the number in the
higher energy state, N-. So according to the Boltzmann equation:

Where
E = Energy difference between the spin states,
K=1.3805x10-23 J/Kelvin (Boltzmann's constant),
T= Temperature in Kelvin
The resultant nuclear magnetism is proportional to
the applied magnetic field.

In the presence of magnetic field (Bo), the energy and the


population difference increase with the applied field Bo.
Larmor Precession

The nuclear magnetic moment may be positive or negative, depending on if the nucleus precesses
clockwise or counterclockwise, respectively. The nuclear magnetic moment will couple to the
external magnetic field, which produces a torque on the nucleus and causes the precession around
the magnetic field.
When placed in a magnetic field, charged particles will precess about the magnetic field. The
charged nucleus, will then exhibit precessional motion at a characteristic frequency known as the
Larmor Frequency. The Larmor frequency is specific to each nucleus. The Larmor frequency
dependent on the magnetic field:

The angular frequency of precession, is the Larmor frequency and is given by and has units of
radians per second.
The larmor frequency depends on the gyromagnetic ratio and the strength of the
magnetic field i.e. it is different for each isotope. For a 1.5 T system, the Larmor
frequency is 63.86 MHz. The Larmor frequency for protons is 21 MHz at 0.5 T and 127
MHz at 3 T.
Subjected to a magnetic field B0

provided to describe the alignment of protons (specifically, hydrogen nuclei) in a 0.5T


magnetic field
1.Total Proton Count: There are 1 million + 2 (or 1,000,002) protons in this scenario.
2.Magnetic Field Strength: The protons are subjected to a magnetic field with a strength of
0.5 Tesla (0.5T). The strength of the magnetic field determines how the protons behave.
3.Proton Alignment:
1. Parallel Alignment: In this scenario, 500,002 protons are aligned in a direction parallel
to the magnetic field. When protons align parallel to the magnetic field, they are in a
lower energy state.
2. Antiparallel Alignment: On the other hand, 500,000 protons are aligned in a direction
antiparallel (opposite) to the magnetic field. This alignment represents a higher energy
state.
NET MAGNETISATION
VECTOR
• Net Magnetisation Vector (NMV)
• The Direction that the protons move to when aligned to the main magnetic
field
• Net sum of protons pointing in the direction of the magnetic field
• Spin up – Spin down = NMV
• Increase B0 = Increase NMV

The intensity or strength of the net magnetization


is influenced by the number of protons present per
unit volume within the sample. In other words, the
more protons there are within a given volume, the
stronger the net magnetization.
BULK MAGNETISATION
• It is good practice to combine the effect of all the
nuclei that are influenced by B0 rather than to
explain the properties of each individual nucleus. The
combined effect of all the nuclei that are in spin-up
and spin-down states is known as bulk magnetisation
(M).
• In equilibrium the bulk magnetisation (M) has only a
longitudinal component aligning along the B0
direction, and it does not produce an MR signal in the
receiver coil. Application of additional radio
frequency (RF) field at the resonant frequency
disturbs M from equilibrium, resulting in the
production of MR signals. In a Cartesian system
which is represented by x, y and z direction, the B0 is
usually represented in the z direction.
NUCLEI IN A STATIC MAGNETIC FIELD
Classical Model

The magnetic moment μ associated with a spinning


spherical charge will precess in an external magnetic
field. In the following illustration, the spinning nucleus
has been placed at the origin of a cartesian coordinate
system, and the external field is oriented along the z-
axis. The frequency of precession is proportional to the
strength of the magnetic field:

ωo = γBo
NUCLEI IN A STATIC
MAGNETIC FIELD
• The diagram illustrates the macroscopic
magnetization of a sample containing large numbers
of spin 1/2 nuclei at equilibrium in a strong external
magnetic field (Bo). A slight excess of +1/2 spin states
precess randomly in alignment with the external field
and a smaller population of _1/2 spin states precess
randomly in an opposite alignment. An overall net
magnetization therefore lies along the z-axis.
• Summation over all spins leads to a magnetization
vector M0 that is parallel to the static magnet field
B0, since more spins are moving on the lower level
cone (blue in Fig) in the equilibrium situation.
• M0 can now be manipulated using an RF excitation
pulse.
NUCLEI IN A STATIC
MAGNETIC FIELD

If rf energy having a frequency


matching the Larmor frequency is
introduced at a right angle to the
external field (e.g. along the x-axis),
the precessing nucleus will absorb
energy and the magnetic moment will
flip to its I = _1/2 state.
NUCLEI IN A STATIC MAGNETIC FIELD
Classical Model

The precessing magnetic moments of nucleus create a


macroscopic net magnetization Mnet a vector quantity having
longitudinal and transverse components that is ultimately
responsible for the induction of NMR signal

However, direct measurement of the magnetization vector is


impossible because it is infinitely small compared to 𝐵₀. To
measure it, it must be tipped into another plane in the x-y
space using a second radiofrequency magnetic field called 𝐵₁.
The 𝐵₁ field enables the transition of spins between the low
and high energy states.
FLIP (OR TIP) ANGLE
• Flip angle, also called tip angle, is the
amount of rotation the net magnetization
(M) experiences during application of a
radiofrequency (RF) pulse. It is often
designated by the Greek letter alpha (α)
and can be measured in degrees (°) or
radians (R). For conversion 360° = 2π
radians.
• For a strong and rectangular RF-pulse of
constant amplitude (B1) and duration (tp),
the resultant flip angle (α) is approximately:

• If γ is expressed in MHz/T, then multiplying


the above result by 360°/cycle will give α in
degrees.
The simple case of a 90° excitation
pulse
The magnetic moment can flip to 90°.

At resonance, during and after excitation the


magnetization vector moves in a complicated way
which can be simplified by using the following trick:

referencing to the resonance frequency

system about the z-axis with frequency ʋ0 leads


Which is identical to a rotation of the coordinate

to a simple rotation of the magnetization vector


about the RF pulse (x-) axis onto the detector
(y-) axis during excitation.
SIMPLE CASE OF A 90° EXCITATION
PULSE

• the system viewed in rotating frame where the frame rotation matches
the Larmor frequency. That is, the frame is rotating exactly at the
same rate as B1, the individual spins, and M.
• The rotation angle depends on the length of time the field is on, and its
magnitude B 1 .
θ = 2π ζ . B 1.

• In our examples, ζ will be assumed to be much smaller than T 1 and T 2.

• A 90 o pulse is one which rotates the magnetization vector clockwise by


90 degrees about the X' axis. A 90 o pulse rotates the equilibrium
magnetization down to the Y' axis.
SIMPLE CASE OF A 90° EXCITATION
PULSE

• Trajectory of an RF pulse excitation with a flip angle of 90◦


a) In the laboratory frame, the net magnetization M0 = Mz precesses on a
spiral trajectory into the x-y plane resulting in a transverse component of
the magnetization Mxy precessing at the Larmor frequency.
b) In the rotating frame, the magnetization is tipped into the x’-y’ plane.
The simple case of a 180° excitation pulse
Quantum model
Energy Transitions (Spin
Flip)
In order for the NMR experiment to work, a spin flip between the energy levels must occur. The
energy difference between the two states corresponds to the energy of the electromagnetic
radiation that causes the nuclei to change their energy levels. The energy of a photon is
represented by
E=hν and ν=γB02π
By applying an RF (radiofrequency) pulse B1, this causes the transition of parallel spins and
the rephasing of protons, resulting in an equal number of parallel and antiparallel spins.
Resulting in population equalization across the two energy levels, and longitudinal
magnetization cancels out
180°
PROBLEMS
EX01: Many magnetic resonance imagers operate at a magnetic field
strength of 1.5 Tesla. A few machine operate at 4.7 Tesla. What is the
resonance frequency of the following nuclei in each of the magnetic fields:
1
H, 23Na 31P?
EX02: What is the energy of the photon that will be absorbed by a 1
H
nucleus in a 1.5 Tesla magnetic field?
• How does this compare in energy to a 2x10 19 Hz x-ray photon?
• Which of the two photons will ionize the molecule?
PROBLEMS
• EX03: A sample has a T 1 of 1.0 seconds. If the net magnetization is set
equal to zero, how long will it take for the net magnetization to recover to
98% of its equilibrium value?
• EX04: A sample has a T 2 of 100 ms. How long will it take for any
transverse magnetization to decay to 37% of its starting value?
• Ex05:A hydrogen sample is at equilibrium in a 1.5 Tesla magnetic field. A
constant B 1 field of 1.17x10 -4 Tesla is applied along the +x'-axis for 50
microseconds. What is the direction of the net magnetization vector after
the B 1 field is turned off?
SOLUTION
EX01:
υ = γBo
• where:
• υ = resonance frequency, γ = gymagnetic ratio for the nuclei in question
and B o = magnetic field strength.
EX02
Given: B o =1.5T o and g = 42.58 MHz/T
• The energy absorbed by a 1 H nucleus is: E H = h n that means E H =hgB o
E H = 6.626x10 -34 Js * 42.58x10 6 Hz/T * 1.5 T H
• E H = 4.23x10 -26
J H E = 4.23x10 -26
J
• The energy of a n =2x10 19 Hz X-ray photon is:
E X = h n E X = 6.626 x 10 -34 Js * 2x10 19 Hz = 1.33x10 -14
J
• How the two energies compare?
• E X / E H = 1.33 x 10 -14 J / 4.23 x 10 -26 J = 3.14 x 10 11
The energy of the X-ray photon is 10 11 times more than the 1 H photon
energy.
• Based on the figure in the text, the ionization potential for an organic
compound is approximately 6x10 -19 J. Therefore only the x-ray photon can
ionize the molecule.
EX03
• Given: T 1 = 1.0s
• The relationship between the equilibrium net magnetization, M o , and the net
magnetization, M z ( t ), at time t is:

M z ( t ) = M o (1 - e - t /T1
).

When M z ( t ) / M 0 = 98%:
• 0.98 = M z ( t ) / M 0 = (1 - e - t /T1
)
• 0.98 = 1 - e - t /T1
• 1 - 0.98 = e - t /T1
• ln( 0.02 ) = - t /T1
• -T 1 * ln( 0,02 ) = t
• -1.0s * ln( 0,02 ) = 3.9s = t
EX04
• Given: T 2 = 100ms.
• The relationship between the initial transverse magnetization (M xyo ) and the
transverse magnetization at any time t , M xy ( t ), is:
M xy ( t ) = M xyo e - t /T2
• When the transverse magnetization (M xy ) has decayed to 37% of its starting
value:
• 0.37 = M xy (t)/M xy0 =e - t /T2

• 0.37 = e - t /T2
• ln( 0.37 ) = - t /T2
• -T 2 * ln( 0.37 ) = t
• -100ms * ln( 0.37 ) = 99.4ms = t
EX05

• Given: B 1 = 1.17x10 -4
T, and t = 50x10 -6
s,

B 1 is applied along the +x' axis.


• The relationship between the rotation angle in radians ( q )and the length, in
seconds, that the B 1 field is applied ( t )is:
q=2ptB1g
• where: g = gymagnetic ratio for the nuclei in question.
• q=2ptB 1 g
• q = 2 p * 50x10 -6
s * 1.17x10 -4
T * 42.58MHz/T
• q = 1.565 rad.
• q = 1.565 rad. * 180 o / p rad = 89.673 o

• The net magnetization vector will be almost along the +y' axis: 89.673 o from the
+z axis after the clockwise about the +x' axis.

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