Bloch equations

Ravinder Reddy
Outline

Magnetic moment and Larmor precession
Bloch equations
With and without relaxation
With RF and Relaxation
Transformation into rotating frame
Steady state solutions
Absorption and dispersion
Steady state solutions
Pulse responses
Advantages and Limitations of BE
Single pulse and spin-echo sequence
Angular momentum and magnetic moment
Consider a charge q moving anticlockwise
On a circle of radius r with velocity v
A charge whose region of circulation is small
compared to the distance at which the eld is
measured is called a magnetic dipole with dipole
moment having absolute value
=iA
Where A is the area of the current loop and i is the
current.
The period of rotation of such particle is t

!=Magnetic moment
v
r
q
t=circumference/speed= 2"r/v
For a circulating charge q, this gives an
equivalent current of
i=q/t=qv/2!r
= (q/2m)/(mvr) m=mass of charge
mvr = L, angular momentum of circulating
charge
=(q/2m) L (magnetic moment is proportional
to angular momentum)
=(q/2m) L =L
=I for the nucleus
Nuclear magnetic dipole moment
Associated with each rotating
object there will be a angular
momentum
Associated with each nuclear spin is
a magnetic moment arising from the
angular momentum of the nucleus
The magnetic moment is a vector
perpendicular to the current loop
In a magnetic eld (B) the magnetic
moment will behave like magnetic
dipole
will experience a torque
"=xB
Larmor Precession

Arclength = (diameter).!.[(d") / 360]
Arclength = radius.(d")

Sin! = r /
r = .Sin!
r
Larmor precession

! =
"I
"t
=
I sin#"$
"t
1 Tesla Magnetic Field ! 42.578 MHz
!
Larmor
= " B
! = ! B = Bsin" = # IBsin"
# = g
e
2m
p
!
Larmor
=
!"
dt
= # B
Larmor Precession
Precession of the
magnetization
vector around the
z-axis of the
magnetic eld
Boltzman factor
Boltzman factor
b=(N
+
-N
-
)/N=E/2kT
K=1.3805x10
-23 J/Kelvin
T=300 k
E= h#=6.626x10
-34
Js x100 MHz
b= 7.99 x10
-6
How is the Boltzman factor changes with B
o
and or T?
Bloch equations
In terms of total angular momentum of a
sample

d!
dt
= "!xB

M=
i
i
!
Total magnetic moment of a sample
Interaction of magnetic moment with magnetic eld gives a
torque on the system and changes the angular momentum of
the system

M = !L

! =
dL
dt
= M " B

dM
dt
= !
dL
dt
= !M " B
Bloch equations
In terms of individual components
d!
x
dt
= " (M
y
B
z
# M
z
B
y
)
d!
y
dt
= " (M
z
B
x
# M
x
B
z
)
d!
z
dt
= " (M
x
B
y
# M
y
B
x
)
BE
Static magnetic
eld is applied along
z-direction. B
z
is
non zero and
B
x
=B
y
=0 and spins
precess around B
z

For free precession in
the absence of
relaxation and RF,
these equations have
to be solved. The
solutions to these
equations are:

M
x
'
= M
x
cos(!t) + M
y
sin(!t)
M
y
'
= M
y
cos(!t) " M
x
sin(!t)

dM
x
(t)
dt
= !M
y
(t)B
z
dM
y
(t)
dt
= "!M
x
(t)B
z
dM
z
(t)
dt
= 0
Including relaxation
Spin-lattice and spin-
spin relaxation can be
treated as rst order
processes with
characteristic times T
1

and T
2
respectively.

dM
x
dt
= ! (M
y
B
z
" M
z
B
y
) "
M
x
T
2
dM
y
dt
= ! (M
z
B
x
" M
x
B
z
) "
M
y
T
2
dM
z
dt
= ! (M
x
B
y
" M
y
B
x
) " "
(M
z
" M
o
)
T
1
Including relaxation terms
alone and treating that the Bo
applied along z-axis (B
x
=B
y
=0,
Bo=B
z
)) the Bloch equations
are given by:


dM
x
dt
= !M
y
B
o
"
M
x
T
2
dM
y
dt
= "!M
x
B
o
"
M
y
T
2
dM
z
dt
= "
(M
z
" M
o
)
T
1
T
1
Solving for M
z


M
z
(t) = M
z
equ
+ [M
z
(0) ! M
z
equ
]exp(!t /T1)
M
z
(t)
M
z
(0)
null t
=
1 T
ln(1!
M
z
(0)
M
z
eq
)
M
z
eq

http://www.cis.rit.edu/htbooks/nmr/inside.htm
Solutions for M
x
and M
y
Solutions for M
x
and
M
y
are:

M
x
(t) = [M
x
(0)cos(!Bt) " M
y
(0)sin(!Bt)]exp("t /T
2
)
M
y
(t) = ["M
x
(0)sin(!Bt) + M
y
(0)cos(!Bt)]exp("t /T
2
)

M
x
(t) = M
0
(0)cos(!Bt "#
o
)exp("t /T
2
)
M
y
(t) = "M
0
(0)sin(!Bt " #
o
)exp("t /T
2
)
These are complicated to visualize
If the magnitude of the
transverse magnetization
at time zero is M
o
and the
angle between M
o
and the
x-axis at time zero is $
o
,
then
NMR signal (~kHz)
Larmor precession frequency (Mhz)
NMR signal (~kHz)
Frequency or Amplitude
modulation
BE with relaxation and RF
Static eld B is
applied along z-
direction B
z
=B
o

and RF eld at
% with an
amplitude %
1
is
applied in the
transverse plane
with components

B
x
= B
1
cos(!t), B
y
= B
1
sin(!t), B
z
= B
o

dM
x
dt
= ! (M
y
B
o
+ M
z
B
1
sin("t)) #
M
x
T
2
dM
y
dt
= ! (M
z
B
1
cos("t) # M
x
B
o
) #
M
y
T
2
dM
z
dt
= #! (M
x
B
1
sin("t) + M
y
B
1
cos("t)) #
(M
z
# M
o
)
T
1
Rotating frame of reference
In the laboratory frame
the magnetization vector
precess at the Larmor
frequecny.
To probe the changes
induced in the frequency
it is convenient to work
in a rotating frame of
reference
In the rotating frame
the magnetization vector,
at equilibrium appears
stationery.
Magnetization vector
Bo is along z-axis
Equilibrium
magnetization Mo is
along z-axis
Mx and My = 0
Rotating frame
In the rotating
frame the
magnetization
appear stationery.
It can only change
in the magnitude in
response to
perturbations
Rotating frame vs Laboratory frame
Magnetization trajectory following RF eld in
Rotating frame
Laboratory frame
Transformation into rotating frame
Additional time dependence introduced in
the form of time dependent RF eld
complicates the analysis.
Two new variables u and v are dened as

u = M
x
cos(!t) " M
y
sin(!t)
v = M
x
sin(!t) + M
y
cos(!t)

M
x
= ucos(!t) + vsin(!t)
M
y
= ucos(!t) " vsin(!t)

= (!
o
" !)v "
u
T
2
Expression for dv/dt can also be obtained similarly

du
dt
=
dM
x
dt
cos(!t) "
dM
y
dt
sin(!t) "![M
x
sin(!t) + M
y
cos(!t)]
= #B
0
v "
u
T
2
"!v
Using Eqn: I
Eqn: I
Rotating frame solutions
Usually u and v are
written as Mx and
My respectively. We
will drop the primes
here and now on we
will work in the
rotating frame with
the following
equations

du
dt
= (!
o
" !)v "
u
T
2
dv
dt
= "(!
o
"!)u + !
1
M
z
"
v
T
2
dM
z
dt
= "!
1
v "
(M
z
" M
o
)
T
1

dM
x
dt
= (!
o
"!)M
y
"
M
x
T
2
dM
y
dt
= "(!
o
" !)M
x
+ !
1
M
z
"
M
y
T
2
dM
z
dt
= "!
1
M
y
"
(M
z
" M
o
)
T
1
Full Bloch equations in rotating frame
Steady state solutions
If we assume that the
system has been allowed to
soak in this combination of
of static and time varying
elds a steady state
ultimately will be reached
in which none of the
components change with
time:

!" = ("
o
#")
"
1
= $B
1
now on we will work in the
rotating frame with the
following eqautions

M
x
=
!
1
T
2
2
"!
1+ !
1
2
T
1
T
2
+ (T
2
"!)
2
M
o
M
y
=
!
1
T
2
1+ !
1
2
T
1
T
2
+ (T
2
"!)
2
M
o
M
z
=
1+ T
2
2
"!
2
1+ !
1
2
T
1
T
2
+ (T
2
"!)
2
M
o
(!
o
"!)M
y
"
M
x
T
2
= 0
"(!
o
"!)M
x
+!
1
M
z
"
M
y
T
2
= 0
"!
1
M
y
"
(M
z
" M
o
)
T
1
= 0
Steady state solutions in the limiting case
In the limiting case
of small RF limit,


!
1
2
T
1
T
2
<<1

M
x
! ("
1
M
o
)
T
2
2
#"
1+ (T
2
#")
2
= "
1
M
o
G(#")
M
y
! ("
1
M
o
)
T
2
1+ (T
2
#")
2
= "
1
M
o
F(#")
The functional forms F
and G are the absorption
and dispersion for a
particular kind of line
known as a Lorentzian
line.



G(!") =
T
2
2
!"
1+ (T
2
!")
2
F(!") =
T
2
1+ (T
2
!")
2
Absorption and dispersion lines
In the limiting case
of small RF limit,

Signal due to M
y
and
M
x
components are
known as absorption
and dispersion,
respectively.
(!T
2
)
-1
Frequency (Hz)--!
Absorption mode
Dispersion mode
Mx and My
Laboratory frame solutions

dM
x
dt
= !M
y
B
o
"
M
x
T
2
dM
y
dt
= "!M
x
B
o
"
M
y
T
2
dM
z
dt
= "
(M
z
" M
o
)
T
1

dM
x
dt
= (!
o
"!)M
y
"
M
x
T
2
dM
y
dt
= "(!
o
" !)M
x
+ !
1
M
z
"
M
y
T
2
dM
z
dt
= "!
1
M
y
"
(M
z
" M
o
)
T
1
Rotating frame solutions

M
x
(t) = M
0
(0)cos(!Bt "#
o
)exp("t /T
2
)
M
y
(t) = "M
0
(0)sin(!Bt " #
o
)exp("t /T
2
)
M
x
(t)
Cos!
or
cos"#t
M
y
(t)
Sin!
or
Sin"#t
Pulsed NMR
Flip angel &
& (rad)=' (rad sec
-1
G
-1
)B
1
(G)t
w
(sec)
http://www.cis.rit.edu/htbooks/nmr/inside.htm
Pulse response
Response of a
pulse duration (t
w
)
and amplitude w
1

applied along x-
axis,
Evolution with a
chemical shift (%
during acquisition

M
x
(+) = M
x
(!)
M
y
(+) = M
y
(!) cos("
1
t
w
) + M
z
(!) sin("
1
t
w
)
M
z
(+) = M
z
(!) cos("
1
t
w
) ! M
y
(!) sin("
1
t
w
)

M
x
(+) = M
x
(!) cos("#t) ! M
y
(!)sin("#t) exp(!t /T
2
)
M
y
(+) = M
y
(!) cos("#t) + M
x
(!)sin("#t) exp(!t /T
2
)
M
z
(+) = M
0
(1! exp(!t / T
2
))

dM
x
dt
= (!
o
"!)M
y
"
M
x
T
2
dM
y
dt
= "(!
o
" !)M
x
+ !
1
M
z
"
M
y
T
2
dM
z
dt
= "!
1
M
y
"
(M
z
" M
o
)
T
1
Pulse response
Following the pulse
M
y
(t)
M
0
Sin!
o
M
x
(t)
M
0
cos!
o

M
x
(+) = M
x
(!)
M
y
(+) = M
y
(!) cos("
1
t
w
) + M
z
(!) sin("
1
t
w
)
M
z
(+) = M
z
(!) cos("
1
t
w
) ! M
y
(!) sin("
1
t
w
)

M
x
(+) = M
x
(!) cos("#t) ! M
y
(!)sin("#t) exp(!t /T
2
)
M
y
(+) = M
y
(!) cos("#t) + M
x
(!)sin("#t) exp(!t /T
2
)
M
z
(+) = M
0
(1! exp(!t / T
2
))
After evolution with the CS
Saturation
If applied B1 is too high the
peak height in the
absorption spectrum is
decreased due to the
reduction in the difference
in population between the
two levels.
This happens when the rate
of energy absorption is
comparable to or greater
than the rate of relaxation
between energy levels, 1/
T1.

!
1
2
T
1
T
2
<<1

!
1
2
T
1
T
2
" 1
http://www.cis.rit.edu/htbooks/nmr/inside.htm
Nuclear receptivity
In Steady state NMR
experiment the spin system
can absorb energy from RF
at a rate R is depends on
transition probability p,
energy level separation, (E
and population difference
(n
o
NMR detected signal ~
dM
y
/dt =R/B
1

R = p!E!n
o
"#
4
B
0
2
NB
1
2
g($) / kT

S ! R/ B
1
!"
4
B
0
2
NB
1
g(#) / kT


!n
o
= N!E / 2kT
p "#
2
B
1
2
g($)
!E = #!B
o

B
1
(opt) = (!
2
T
1
T
2
)
"1/ 2
Limitations of BE
Can not be used to
analyze other
interactions such as J-,
dipolar and quadrupolar
2D NMR
Higher spin (I>1/2)
interactions
MQ coherences can not
be explained
Molecular motional
processes (T1 and T2) and
eld inhomogeneity
Gradient manipulation and
MR imaging