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Wave-particle Duality
34
10
Particles also show wave-like properties
Wave-length = Energy=
=frequency, =momentum, =6.6 Js Planck's constant.
h
hf
p
f p h
=
=
= +
=
= = =
= = =
= =
( )
- , - 1 ,...., 1,
(2 1)
Component along one direction:
different states.
z l l
L m m l l l l
l
= =
+
2
where
h
=
Where is the electron ?
Wave functions
Current loops and magnetic dipoles
-
+
N
S
Current loop
Bar magnet
Orbiting electron as a current loop
2
1
2 2 2 2
2
Tiny current loop.
charge
current
period
Magnetic moment
area of loop
Angular momentum:
(parallel to angular momentum)
Gyrom
e
l
e
dq e
I
dt T
IAn
A
v ev ev evR
IA A R
T R R R
L m vr
e
L
m
= = =
=
=
= = = = =
=
=
2
agnetic ratio: =-
l
e
e
L m
=
e
R
= = =
= = =
= = =
= = =
shifted energy one state with no energy shift. +
2
z z
B
(1)
(2)
(3)
l=0
l=1
( ) ( )
2
2 2 2 2 2 2
,
1
What happens when a circulating electron is placed
in a magnetic field.
We know that are fixed and known.
constant
By symmetry, same spread of results of
or when mea
Z
x y Z l
x y
L L
L L L L l l m
L L
+ = = + =
sin
1 1
sin
sin sin
2
2
surements of made.
i.e. just as likely to find angular momentum and .
Magnetic field introduces a torque
=
i.e
l l
l
l
e
l
e
X Y
dL
B B
dt
B d dL
B
dt L dt L L
m eB
L
e m
= = =
= = =
= =
.
2
. the angular momentum vector precesses around the magnetic
field ( -axis) with frequency This is Larmor precession.
Gyromagnetic ratio :
e
z
e
B m
= =
L
Z
U
X
x
y
z
Angular momentum precession
L
Z
constant and L precesses around z-axis
Question
.
Is it possible for an electron in a hydrogen atom to have ?
Show that this value can be approached for large values of
Would be possible using classical physics ?
No - it can never happen o
Z
Z
L L
l
L L
=
=
( )
2 2 2 2 2
,
0
1
therwise we would "know" values of
i.e.
For large
Max
(comes close)
In classical physics there is no restriction on what we can and ca
x y
x y
Z l Z
Z
L L
L L
L l l l L l L l
L m L l
L L
= =
= + = =
= =
n't know.
The mathematics of spin angular momentum is identical to orbital
angular momentum.
F
N
F
S
F
N
F
S
Magnetic field
Magnetic field
Ignore force not parallel to North-South axis.
Magnetic field
Magnetic field
Magnetic field
Zeeman effect with orbital and spin
angular momentum
In the presence of
a magnetic field,
multiplicities of
spectral lines
appear
1
0
2
2 1 2
Eg for ,
number of lines:
l s
n s
= =
= + =
2
B
B
2
2
Identical to orbital case.
;
spin magnetic moment
Electron:
electron g-factor 2, electron mass.
Nucleus:
nuclear g-factor, proton mass.
(ne
s
s
e e
e
e e
N N p
p
S B
e
g
m
g m
e
g g m
m
= =
=
=
= =
= = =
xt lecture)
S
Z
x
y
z
Larmor precession for spin
S sin
S
Summary
Established basic quantum mechanics
theory needed for NMR
wave-particle duality
Light is either photons or electromagnetic waves
Schrdingers equation and the wave function
at the heart of QM predictions
Energy and angular momentum are quantised
Larmor precession
Angular momentum comes in two varieties
(orbital and spin)
The Quantum Mechanics of MRI
Part 2: Understanding MRI
David Milstead
Stockholm University
Outline
Spin - reminder
Fermions and bosons
Nuclear energy levels
2 2
( 1)
2
2
Identical in form to orbital case.
spin magnetic moment
Electron:
electron g-factor 2, electron mass.
Nucleus:
nuclear g-factor,
z s
s
s
e e
e
e e
N N
p
S s s S m
B
S
e
g
m
g m
e
g g
m
= + =
=
=
=
=
= =
= =
proton mass.
(next lecture)
p
m =
S
Z
x
y
z
Spin
S sin
S
Gyromagnetic ratio
Why do they have different values ?
Fermions and bosons
Fermions
Spin 1/2, 3/2, 5/2 objects
Electrons, protons and neutrons have spin 1/2
Tricky bit comes when combining their spins
to form the spin of, eg, an atom or a nucleus
Bosons
Integer spin objects
Similar shell structure for nuclear
physics as for atomic physics
Need to fill up, shell by shell
Pairs of protons and neutrons cancel
each others spins.
Paulis exclusion principle ensures
that many shells are filled.
Nuclei with uneven (even) atomic
number have half-integer (integer)
spin
Nuclei with even atomic and mass
numbers have zero spin.
Unpaired neutrons/protons provide
the spin for MRI.
Question
Nature would prefer all electrons to be in
the lowest shell and all nucleons
protons/neutrons) in the lowest shell ?
Why doesnt this happen ?
Usefulness for MRI
Need isotopes with unpaired protons (to
produce signal for MRI)
Most elements have isotopes with non-
zero nuclear spin
Natural abundance must be high enough
for MRI to be performed.
Spins of various nuclei
Now we can understand MRI
0
1
1 0
?
We know the basics:
A uniform magnetic field B
A short pulse of a rf field B
A system out of equilibrium
measurement of return to equilibrium.
Why is
(a)
(b) The rf pulse shorter than recovery
B B
<<
time ?
No magnetic field
Apply an external magnetic field
.
, 0
1
2
Spins precess at Larmor
frequency
Gyromagnetic ratio:
Precessions incoherent:
Total spin
Z x y
Z
B
S S S S
S
=
= = =
=
B
0
In fact, there are continual transitions
and interactions from thermal energy.
Another look at the system
Split into spin-zones.
For uniform system we can regard the macroscopic system as giving
a single magnetisation.
Conventional to talk about magnetisation :
; no. dipoles, volume
s
M
N
M N V
V
= = =
Putting together what weve learned
0
0 0 0
,
2
1
2 2 4
2
2
Need to know its energy splitting.
=spin angular momentum nuclear g-factor proton mass.
;
Frequency of light need
s
N p
p
sZ sZ z N N
p p
p
sZ
p
e
g S g m
S m
e e
E B S g g
m m
g e
E B B
m
= = = =
= = = =
= = =
0 0
0
0 0
2
2
ed for excitation
Larmor frequency:
How many nuclei can be excited ?
p
p
N
p
g e
B
m
eB
B g
m
=
= = =
0
0
Energy level population
Nature has a preference for the lowest energy states.
In thermal equilibrium the lowest states are a bit more
populated than the higher energy states.
2
23
0 0 0
6 26
0
1 ...
2!
1
2
1.5 42.576 10 2 4.2 10
Taylor expansion:
Boltzmann's constant = 1.38 10 J/K
=room temperature 310 K
T J
x
B B
B
p
p
x
e x
N E E
e
N k T k T
k
T
g e
E B B
m
B E
N
N
= + + +
= +
=
= = =
= = =
0
1.000009
1
2 2
p
p B
g e N
N
N N N N B
N m k T
=
= =
Changing the spin populations
15
Tiny differences in, eg, 0.02ml of water
expect 610 more in parallel state.
Question
Chemists can excite certain samples using UV light. Would you expect
to be substantially different in this case ? What does this imply for
the relative size of the sample of a MRI scan and a test
N
N
8
8 16 1
8
34 16 17
17
23
3 10
10 3 10
10
6.6 10 3 10 2 10
2 10
1 1 1 5000
1.4 10 300
made by
chemists with infrared light ?
UV-light m s
J
In fact, approximation no longer valid since it
B
c
f
E
N E
N k T
= = =
=
+ + +
is no longer a
small difference!!
A chemist can use far smaller samples since the energy gap
is larger and there are far more in the lower energy state.
Exciting the nuclei - Rf pulse
Rotating magnetic field B
1
Typical pulse duration ~1ms.
Two ways to think about the pulse. Both are needed to understand MRI.
Excitation
Rotating magnetic field B
1
B
0
Pulse of rf-
1
0.
The rf pulse acts in two ways:
(1) The photons are absorbed, saturating the system and reducing
(2) The rotating magnetic field acts on the magnetisation vector
to rotate into the complex plan
Z
M
B
1 1
1
1
1
e.
Individual dipole: ;
Use magnetisation: - simple form of the Bloch equations.
s
s s
d dS
B B
dt dt
dM
M B
dt
= = = =
=
B
1
Rotating frame of reference
, ', '
'
Easier to understand if a rotating frame of reference
(with Larmor frequency) is used.
Rotate co-ordinates
Magnetic field constant on axis.
x y x y
x
B
0
B
1
X
y
Different types of pulses
90
o
180
o
1
1
1
5
1
3 6
0
2
2 42.58
1 1
10
10 42.58 10
1
Duration of pulse and size of B determine angle of rotation of magnetisation:
Spins precess around
Consider a full rotation of in 1ms
MHz/T
T
B
B
t
B
B T
= =
=
=
=
1 0
. B B <<
Question
1
1 0
.
When applying a new magnetic field is obtained:
Why don't the protons just align with respect to that field ?
n
B
B B B = +
0
B
n
B
What happens next ?
-
.
Consider a 90 rotation.
The magnetisation vector is in the plane.
The -pulse is turned off.
The system must return to equilibrium.
We have two components: and
o
Z xy
x y
rf
M M
Longitudinal relaxation
Spin-lattice effect:
higher energy state interacts with lower energy state due and lose
energy through rotation and vibration .
Relaxation times for different materials
Transverse relaxation
In the laboratory frame
Dipole moments are initially in phase.
M precesses and decays.
As it precesses phase decoherence occurs.
Complicated process: contributing factor non-uniform magnetic
field ove
xy
r sample different precession rates for different regions.
Free induction decay
*
2
.
As the transverse magnetisation decays, a changing magnetic
field is produced:
=- an emf is produced in a receiver.
The signal is a decaying sinusoidal wave with lifetime
Measurement of gives
t
T