2
This represents the kinetic energy of a single particle in the
rotating body; the total energy of all the particles is:
E
k
=
1
2
mr
2
2
The angular velocity, w, is constant for all particles and the
summation of
mr
2
is called the moment of inertia and is analogous to
our familiar concept of mass:
I =
mr
2
So:
E
k
=
1
2
I
2
[124]
which now looks much like the translational kinetic energy equation.
When considering translational motion and work we generally use
force, F, and distance (or displacement), s, to calculate the work
done. Again, the rotational version of this calculation is very
similar. Distance, s, is replaced by an angle, , and force is
replaced by torque, :
W= [125]
The net work done is the change in kinetic energy:
dW=d=d(
1
2
I
2
)=
1
2
I d
2
=
I
2
d
2
d
=I
d
d
=I
d
dt
d
d
=I
d
dt
=I
=I
This leads us to angular momentum:
=I =I
d
dt
=
d(I )
dt
The product of I and is the rotational analog of momentum for
translational motion and is given the symbol L.
=
d(I )
dt
=
dL
dt
dt =dL
[126]
Ok .. so far there should not have been any great leaps in logic (as
long as you have your calculus wits about you).
Now, let's look at some vector quantities. First, consider a
tangential force vector,
F at a distance r from the center of rotation
and a distance vector r as in the following figure. It is apparent
that this force will change the rotational velocity and the angular
momentum. Again, this is analogous to the translational motion
situation.
Now consider what would happen if
F were to be directed not
tangentially but orthogonally. In other words, if
F were to be
directed parallel and colinear with r there would be no change in the
torque (however, see below). This is just what one would expect of a
vector relationship between r and
F . Thus we write the vector cross
product:
=r
F
[127]
Here, the magnitude of the torque is:
=rF sin()
where is the angle between r and
F . A 3D picture helps us to see the
relationships.
Figure 122:Tangential
force vector,
F
F
r
When
F is tangential then sin() is 1 and the torque is simply rF. When
F
is colinear with r , sin() is 0 and the torque is zero. Note that here
the torque is directed along the axis of rotation (however, see
below).
Similar considerations for linear and angular momenta lead us to:
L=rmv
=rp
[128]
where p is linear momentum. As with the torque,
L is directed along the
axis of rotation. We can also represent r analogously to p in linear
mechanics:
p=mv
L=I
Figure 123:Vector
relationships, radius,
force and torque
F
r
I=rF
I
Figure 124:Tangential
momentum
mv
r
This of course implies that lies along the axis of rotation. A
moment's thought will convince you that this must be so. For a
rotating body with no external forces acting on it, is constant. If
this is so then it must be directed along the rotation axis since any
other direction would imply that it changes direction with the
rotating body and therefore is not constant. A similar argument
applies to , the angular acceleration and angular momentum,
L . It
seems strange at first that these vectors are not pointed in the
direction of movement but it must be so for them to be constant.
We have seen, above, what happens when there is a tangential force
applied to the rotating body. A torque proportional to the force and
its distance from the rotation axis is generated and is directed
along the axis of rotation. In other words, the magnitude of the
torque changes, but not its direction (unless the force changes
direction).
It is possible to have two forces applied simultaneously to the
rotating body.
Figure 125:Vector
angular velocity and
torque
w a
L G
r
In this case the two forces are of equal magnitude and opposite
direction and are called a couple of moment. One encounters this
situation for example, when using a compass. What is the torque on
the system?
=2r
F
=2rF
[129]
Since the two forces in the diagram are tangential the angle between
r and F is 90 degrees and the magnitude of the torque is at a
maximum. Also, from the right hand rule, the torque vector is coming
out of the page towards you. If the angle that F makes with r changes
from 90 degrees the torque decreases as in the compass example.
What happens if the force,
F , is directed along a line that
passes through the axis of rotation? We have already seen that this
must not change the magnitude of the torque. There is, however,
another effect which is of pivotal (pun intended) importance to us,
called precession.
Understanding this concept requires some pretty complex 3D
visualizations. Here is the basic (somewhat crowded!) picture:
Figure 126:Simultaneous
tangential forces
F
r
r
F
This is the example of the spinning top. There is a force, mg , on the
rotating body that goes through the axis of rotation. The torque is:
=r
F
=rmg
This vector cross product will be orthogonal to the plane defined by
r and mg . From equation [125], the torque is related to the angular
momentum or rather, the rate of change of the angular momentum. This
being the case, we see that d
L (not
L !) is in the same direction as
the torque and is at right angles to the angular momentum,
L . As the
top spins about its axis of rotation the torque causes it to precess
about an axis of precession. This is the source of the wobbling
motion of a top. Note that in the case of a force at right angles to
the axis of rotation and not passing through the axis of rotation
causes a change in the magnitude of the angular momentum but a force
passing through the axis of rotation causes a change in direction of
Figure 127:Torque, force and precession
mg
r
L = Iw
q
q
dL
Lsin(0)
d
I
the angular momentum.
The Magnetic Moment
The idea of the magnetic moment is pretty simple and comes from
some basic observations of the physical nature of electric currents
and magnetic fields. We wish here to describe the interaction between
a magnetic moment and a static magnetic field and also with other
magnetic moments. The most basic observation is that a charge, q,
moving through a magnetic field,
B , with velocity, v experiences a
force,
F , which is directed at right angles to both v and
B :
The vector equation for this is (see equation 106):
F=qv
B
[1210]
This is, of course, a vector crossproduct from which we can get
the magnitude of
F quite easily (see equation [316]):
F=qvBsin()
where is the angle between v and
B as in figure 98. We can write the
vector equation in terms of infinitesimals:
d F=dq(v
B)
Figure 128:Force on a charged
particle
f
B
qv
F
and since v represents the linear velocity of charge per unit time,
d
l
dt
, we can write:
d
F=
dq
dt
(d
B)
If we integrate over the length of the wire to get the total force of
the current we get:
F=i
B
[1211]
Where i=
d q
d t
.
Now, if
l and
B are at right angles to each other then we can
calculate the magnitude of F directly:
F=ilBsin(
2
)
=ilB
where i is the current, l is the length of the wire and B is the
magnitude of the magnetic field. We assume that B is constant over the
length of the wire.
Now, let's take things a step further and imagine a current
conducting coil in a magnetic field at an angle , to the field,
B :
The first diagram is a side view of the coil which is at an angle to
the field,
B , and is able to rotate about an axis coming out towards
the viewer. The second is a left view. Here, the field,
B , in the
second diagram is directed away from the viewer into the page as
indicated by the x's. In other words, the top diagram has been turned
counterclockwise as seen from the top to get the bottom diagram. The
current carrying coil is rectangular in shape with sides of length a
and b. From equation [1211] the force, F, is then given by:
F=iaB
assuming a current of i amperes moving through the coil and that the
field,
B , is at right angles to the movement of current. The force on
sides b is:
F' =ibBsin()
Forces F' on sides b cancel each other. Forces F are equal in
magnitude but are not colinear (top diagram) so that they constitute
a couple of moment. From equation [129] the torque that this
produces is:
Figure 129:Electric current loop
in a magnetic field
B
F = iaB
F = iaB
x x x x x x
x x x x x x
x x x x x x
x x x x x x
x x x x x x
a
F
F
b
F' F'
side
view
left
view
f
o
o
=2r
F
=2rFsin()
=2
1
2
bF sin()
=bFsin()
=iaBbsin()
which will cause the coil to begin to rotate. The torque vector will
be along the axis of rotation which, in the diagram, is colinear
with F'. a times b is the area inside the coil so:
=iABsin()
where A represents the area. i
B
=
d
L
dt
[1212]
A commonly used term is the gyromagnetic ratio (or the
magnetogyric ratio depending to whom you are talking). For a
classically spinning (periodic) system we can calculate what this is:
=i A
=
q
t
r
2
=
qv
2r
r
2
(t =
2r
v
)
=
q
2m
mvr
=
q
2m
L (eq. 88)
q/2m is the gyromagnetic ratio.
=
q
2m
L
=L
[1213]
or in vector and differential form:
=
L
d
dt
=
d
L
dt
=(
B)
[1214]
We see from this that the magnetic moment is proportional to the
angular momentum with the constant of proportionality being g.
Finally, we are in a position to discuss the magnetic moment of
a spin which, as nmr spectroscopists, we are naturally very
interested in. The really fascinating feature of spins is that they
contain intrinsic angular momentum as a fundamental property in the
same way that mass and charge are fundamental physical properties.
Hence the use of the word spin. This is a property of matter that
was wholly unknown less than a hundred years ago.
Our spin is labeled with its magnetic moment, and the external
magnetic field as
=
d
L
dt
=
B
or:
d
L=
dt
=
Bdt
we can use the gyromagnetic ratio:
d
L=
Bdt
d=(
B)dt
and
du=Bsin()dt (from figure 810)
Figure 1210:Magnetic moment of a
'spin' in an external magnetic
field
sin(0)
=y
L
B
0
d
d
Also from the figure (and eq. [121]):
d=sin( )d
= Bsin ()dt
and therefore:
d
dt
= B
=
d
dt
= B
[1215]
where is the angular precession frequency. Why the negative sign?
From figure 810 the direction of precession is lefthanded compared
to the direction of
B . Using the right hand rule and aligning the
thumb with
B , we see that the 'positive' direction is opposite to
that of
d
d t
. is the Larmor freqency of precession of a spin and
equation 1214 is the Larmor equation. Thus, if we know the values of
the gyromagnetic ratio and the applied field we can calculate the
precession frequency. For a proton in a 11.7 Tesla field this turns
out to be 500 MHz. Just to confuse things, the preceding applies to
nuclei with a positive g .. things are opposite for nuclei with a
negative g.
The energy of a magnetic moment in an external field may be
calculated using the differential version of equation [125]:
dW=d
and doing the indefinite integral, we get:
W=
d
=
Bsin()d
= Bcos()+C
If we arbitrarily take the zero point of energy to be at q = 90
o
then
we can write for the energy:
E= Bcos()
or, in dot product vector notation:
E=
B
[1216]
This is a fundamental equation in nmr spectroscopy, needed for
building the quantum mechanical Hamiltonian operator. Amazingly it is
usually simply stated and is not derived in many (if any) nmr texts.
The definite integral of the above energy equation [1216] done
between q = 0 and q = p gives the energy difference between the
lowest and highest energy of the spinning magnetic moment:
W=
Bsin()d
= Bcos()
0
=2 B
Equation 915 expresses the classical energy associated with the
interaction of a magnetic moment and a static magnetic field. We now
are tempted to ask what is the classical energy of interaction of
two magnetic moments,
1
and
1
?. One might suspect that the the
required expression is similar to equation 915 since each magnetic
moment 'feels' the field of the other. This is so. The derivation of
this expression is somewhat tedious so we will simple state the
expression here. The curious reader may, however, consult the
literature in the references; in particular, Weil, Cheston or Atkins
discuss this in varying levels of detail. The energy expression is:
E=
0
4
3cos
2
()1
r
3
1
2
The Bloch Equations
This topic is one of the worst developed in many nmr texts.
Almost invariably the text will more or less simply state 'here they
are' without much logical development and perhaps refer the reader to
Bloch's original paper. The problem with this is that Bloch did a
notsogood job of explaining them too! Fortunately, others (see
references) have published papers in which Bloch's equations are
rather more readably solved for various situations. We will also try
to produce them in a logical fashion below.
Using the ideas just developed concerning magnetic moments and
angular momentum, we can develop a description of the time evolution
of nuclear magnetic moments or just the nuclear magnetisation. These
equations are named after Felix Bloch, one of the giants of early nmr
spectroscopy along with Edward Purcell and Isador Rabi.
So far, we have considered only a single spin and its magnetic
moment. What about a large collection of spins that have been placed
in a magnetic field? We define now a quantity called the bulk
magnetic moment. This is the macroscopic version of the microscopic
magnetic moments of the nuclei in the sample and is the vector sum of
all magnetic moments in the bulk of the material of interest:
M=
i
N
i
[1217]
Pictorially this looks something like:
Of course, at the instant that they are put into the field there will
be a completely random distribution of magnetic moments in all
directions. The bulk magnetic moment (or net magnetisation or net
polarisation in nmrspeak) is therefore zero. After some time however
this changes and a net magnetic moment, M, appears, aligned with the
external magnetic field,
B
0
, and the spin system is said to be at
equilibrium. Chapter 14 deals with the mechanism of this process in
more detail.
Figure 1211:Randomly oriented
magnetic moments
x
y
z
Now we look closely at this net magnetisation. At equilibrium
this magnetisation vector is aligned parallel to the zaxis as is the
external magnetic field,
B
0
. Note that we are now subscripting
B since
we will shortly be dealing with two different magnetic fields and
must keep track of which one we are talking about. We will label the
magnetisation vector in the equilibrium state as
M
0
. Imagine that we
now move this vector away from its equilibrium position in some as
yet unspecified way and that the vector, now labeled
M since it is
not in the equilibrium position, is not colinear with the x, y or z
axes. We can break
M down into its component vectors along the axes:
Figure 1212:Excess spins oriented
with the external field and net
magnetic moment,
M
0
x
y
z
M
0
Vector
M , being at an angle with respect to the zaxis and therefore
the applied field
B
0
, will precess about the zaxis, just as the
individual magnetic moments will. Assuming that there will no
relaxation of
M back to the equilibrium position along the zaxis and
that it will precess indefinitely we can write:
d
M
dt
=
M
B
0
[1218]
which is the macroscopic version of equation [1213]. Using our
determinant method (eq. [23]) to expand this we get:
d
M
dt
=det
u
x
u
y
u
z
M
x
M
y
M
z
B
0x
B
0y
B
0z

=(M
y
B
0z
M
z
B
0y
) u
x
(M
x
B
0z
M
z
B
0x
) u
y
+(M
x
B
0y
M
y
B
0x
) u
z
=(M
y
B
0z
) u
x
(M
x
B
0z
) u
y
+0 u
z

=(M
y
B
0z
) u
x
(M
x
B
0z
) u
y

[1219]
Figure 1213 Component vectors of M
M
x
M
z
M
y
x
y
z
remembering that the field
B
0
is parallel to the zaxis and has no
components in the xy plane. ux, uy and uz are of course unit basis
vectors. This result tells us that the magnetisation changes in the
xy plane but not along the zaxis. In other words the magnetisation
vector,
M , precesses about the zaxis as shown in the figure. Since
the projection of
M onto the zaxis will (obviously) not precess
about the zaxis we can write:
d
M
z
dt
=0
or:
d M
z
dt
=0
[1220a]
This should also be evident from the fact that
d
M
dt
is at right angles
to the plane defined by
M and
B
0
and will therefore have no component
on the zaxis. M
z
is called the longitudinal magnetisation.
What about the magnetisation in the transverse (the xy) plane?
Equation [1218] indicates that all of the change in
M is in the
transverse plane. From [1218] it is reasonable to write:
dM
x
dt
= M
y
B
0z
= M
y
0
[1220b]
using the magnitude of the xcomponent of
M and equation [1215].
Also:
dM
y
dt
= M
x
B
0z
=M
x
0
[1220c]
Combining equations [1219] into a vector equation:
d
M
dt
=
0
M
or
d
M
dt
=
M
B
0
[1221]
where we have used the relation (eq. [1215]):
0
=
B
0
or
B
0
=
0
[1222]
You might be forgiven for asking where did the negative sign
come from?. This is a bit of a puzzle since, yet again, many texts
treat this very loosely or not at all. However, it is really very
simple:
d
M
dt
=
0
M
=
M
0
=
M(
0
)
=
M
B
0
=
M
B
0
Equations [1220] and [1221] refer to the special (and artificial)
case in which there is a magnetisation
M in an external field
B
0
and
there is no relaxation taking place. They do however serve as a
starting point for our further deliberations.
Before we take into account relaxation let's look at the
situation when a linearly oscillating electromagnetic field,
B
x
,
moving back and forth along the xaxis is applied at right angles to
the external field,
B
0
. Conceptually, the
B
x
field may then be broken
up into two counterrotating vectors the sum of which always is
B
x
.
We will call these new vectors
B
1L
and
B
1R
for the moment and assign a
rotational frequency of +
1
and
1
to them. The x and y components of
these two counterrotating vectors are contained in:
B
1R
=B
1
u
x
cos(
1
t )+ u
y
sin(
1
t )
B
1L
=B
1
u
x
cos(
1
t ) u
y
sin (
1
t )
B
1R
+
B
1L
=2B
1
u
x
cos (
1
t )=
B
x
[1223]
where
B
1R
uses +
1
and
B
1L
uses
1
.
Only one of these two
B
1
fields will concern us since the other
is rotating with a negative frequency relatively speaking and does
not affect any spins. We choose one and ignore the other. Let's
choose
B
1R
and simply call it
B
1
for the rest of the discussion.
So, now we have two fields to consider,
B
0
and
B
1
.
B
0
is, of
course, static and aligned along the zaxis (or more accurately, the
zaxis is aligned with
B
0
) and
B
1
is at 90 degrees to the zaxis and
rotating about the zaxis at
1
radians per second. We can call the
sum of these two vectors
B
eff
:
Figure 1214:Counterrotating applied
magnetic fields
B
1R
x
y
z
B
1L
B
x
B
0
Obviously, since
B
1
is rotating about the zaxis,
B
eff
is rotating
about the zaxis as well. The size of
B
1
is much exaggerated in the
figure. Generally,
B
1
<<
B
0
so that
B
eff
is only slightly off of the z
axis. Our new simple Bloch equations (still without relaxation taken
into account) are:
d
M
dt
=
M
B
eff
=
M(
B
0
+
B
1
)
=
M
B
0
+
M
B
1
=det
u
x
u
y
u
z
M
x
M
y
M
z
B
0x
B
0y
B
0z

+det
u
x
u
y
u
z
M
x
M
y
M
z
B
1x
B
1y
B
1z

=(M
y
B
0z
M
z
B
0y
) u
x
+(M
y
B
1z
M
z
B
1y
) u
x
(M
x
B
0z
M
z
B
0x
) u
y
(M
x
B
1z
M
z
B
1x
) u
y
+(M
x
B
0y
M
y
B
0x
) u
z
+(M
x
B
1y
M
y
B
1x
) u
z
=(M
y
B
0z
M
z
B
1y
) u
x
(M
x
B
0z
M
z
B
1x
) u
y
+(M
x
B
1y
M
y
B
1x
) u
z
remembering that
B
0
is along the zaxis and
B
1
is in the transverse
Figure 1215:Effective magnetic field
B
1
x
y
z
B
0
B
eff
plane and therefore B
0x
, B
0y
and B
1z
are zero. The rates of change of
each component of
M are:
d M
x
dt
=(M
y
B
0
M
z
B
1y
)
d M
y
dt
=(M
x
B
0
M
z
B
1x
)
d M
z
dt
=(M
x
B
1y
M
y
B
1x
)
[1224]
B
0
and B
0z
are equal since
B
0
is colinear with the zaxis ... hence
the change from B
0z
to B
0
in [1223]. Using equation [1222] we can
modify [1223]:
d M
x
dt
= M
y
B
0
M
z
B
1
sin(
1
t )
d M
y
dt
= M
x
B
0
M
z
B
1
cos(
1
t )
d M
z
dt
= M
x
B
1
sin (
1
t )M
y
B
1
cos (
1
t )
[1225]
Again, note that these equations do not include relaxation and assume
the presence of
B
0
and
B
1
.
We have introduced the oscillating
B
1
field without saying why.
Something completely astounding and counterintuitive happens when we
do this! First, let's invoke the rotating frame of reference.
Specifically, let's use equation [344] and our magnetisation vector:
(
d
M
dt
)
LAB
=(
d
M
dt
)
R!
+(
1
M)
or
(
d
M
d t
)
R!
=(
d
M
dt
)
LAB
(
1
M)
Recall from equation [344] that(
M ) refers to the rotation of the
x,y and zaxes at vector frequency . We are completely free to
choose what that frequency is so we choose the frequency of the
rotating
B
1
field,
1
.
We also realize that the LAB portion of this equation can be
replaced by [1220]:
(
d
M
d t
)
R!
=(
o
M)(
1
M)
or
(
d
M
d t
)
R!
=(
M
B
0
)+(
M
1
)
=
M(
B
0
+
1
)
=
M(
B
0
+
1
)
[1226]
Note that, since the order of
M and
1
were reversed, the sign of their
cross product changes.
Let's put
B
1
into the equation now:
(
d
M
d t
)
R!
=
M(
B
0
+
1
B
1
)
and define a 'fictitious field' (using [1221]):
B
fic
B
0
+
1
=
0
+
1
=
1
0
[1227]
and put it into the equation:
(
d
M
d t
)
R!
=
M(
1
0
B
1
)
=
M(
B
fic
+
B
1
)
=
M
B
r
[1228]
where
B
r
is the resultant field. This is the equation of motion of the
magnetisation in the rotating frame and has exactly the same form as
our previously developed equation for the laboratory frame, equation
[1221].
So, we have
0
and
1
and
M and
B
1
.
0
is the Larmor frequency of a
spin in the static field,
B
0
and is itself constant.
M is the
magnetisation due to the sum of the magnetic moments in the
collection of (many, many) spins in the sample.
B
1
is the rotating
magnetic component of the applied electromagnetic field.
1
is the
frequency of the rotating frame of reference which is also the
frequency of the
B
1
field.
What will happen if we vary
1
from zero up to
0
? The term
1
0
B
r
is entirely in the xy plane. In other words,
B
fic
vanishes! Thus
when the frequency of irradiation is equivalent to the Larmor
frequency of the spin the external field vanishes from the rotating
frame of reference. Amazing!
Furthermore, if we vary
1
slowly the magnetisation,
M , will
precess about
B
r
and end up precessing about
B
1
in the transverse plane.
When
1
0
=0 we say that we are at (or on) resonance ... hence the
name, nuclear magnetic resonance. Also, since
M now sees no external
field in the rotating frame its internal precession frequency about
the zaxis is zero relative to the rotating frame. You can see this
in equation [1227] when
1
0
=0 .
Figure 1216:Resultant
magnetic field
B
1
B
fic
B
r
Our equations so far have assumed the projections of
M onto the
laboratory frame axes, M
x
, M
y
, and M
z
(figure 1213). We ask now, what
are the projections of
M and
B
r
onto the rotating frame? We assume that
the rotating frame frequency is that of
B
1
and that
B
1
is aligned along
the rotating x'axis. We will use x' and y' to denote the rotating
axes and x and y for the static axes. Of course, the zaxis is the
same in both frames.
Figure 1217
x
y
z
B
fic
x'
y'
B
1
Figure 1217 shows that
B
1
is aligned along the x'axis and
B
fic
is
aligned along the zaxis. Figure 1218 shows the vector components of
B
r
=det
u
x'
u
y '
u
z
M
x
' M
y
' M
z
B
1
0
(
1
0
)

=(M
y'
(
1
0
)
) u
x'
(M
x '
(
1
0
)
M
z
B
1
) u
y '
M
y '
B
1
u
z
[1229]
The components of
d
M
dt
along the (rotating) coordinate axes are:
d M
x'
dt
=M
y '
(
1
0
)
[1230a]
Figure 1218
x
y
z
x'
y'
M
x'
M
y '
M
z
d M
y '
dt
=M
x'
(
1
0
)+ M
z
B
1
[1230b]
d M
z
dt
= M
y '
B
1
[1230c]
These are the Bloch equations 'anchored' to the rotating frame
as it were, rather than the laboratory or static frame (equation [12
24]). Note that the sine and cosine terms are gone. This is
reasonable since
B
1
is now 'motionless' in the rotating frame and
therefore should naturally be expected to be timeinvariant in this
frame of reference.
Now, finally, we will include relaxation. What is relaxation? As
it turns out, there are two types that will be of interest to us.
First, if you do an inversion recovery experiment you can watch the
change of M
z
from nonequilibrium back to equilibrium where it is
equal to M
0
. The description of this experiment is beyond the scope
of this document but there are many good references to it. The change
from nonequilibrium to equilibrium is, as it turns out, an
exponential one and we can model it as:
M
0
M
z
=Ae
t
!
1
or
ln(M
0
M
z
)=A'
t
!
1
where M
0
is the equilibrium magnetisation (and is constant) and M
z
is
the magnetisation at time t (and is therefore variable). We model it
this way so that we have positive quantity that decays towards zero
in an entirely analogous way to radioactive decay. A and A' are
constants whose values we need not be concerned about here since they
will disappear. Now, differentiating with respect to time:
1
M
0
M
z
d M
z
dt
=
1
!
1
or
d M
z
dt
=
M
0
M
z
!
1
[1231a]
Don't confuse this with equation [1225]! Equation [1231a] refers to
the rate of change of M
z
due to relaxation processes only. What about
M
x
and M
y
? If we think a bit about what must happen when M is tipped
away from the zaxis.
In the xy plane there is a similar (mathematically) decay.
Magnetisation here decays according to:
M
x
=A e
t
!
2
or
ln(M
x
)=A'
t
!
2
1
M
x
d M
x
dt
=
1
!
2
d M
x
dt
=
M
x
!
2
[1231b]
and similarly:
d M
y
dt
=
M
y
!
2
[1231c]
If we add these in to our current Bloch equations ([1230])we
get:
d M
x'
dt
=M
y '
(
1
0
)
M
x '
!
2
[1232a]
d M
y '
dt
=M
x'
(
1
0
)+ M
z
B
1
M
y'
!
2
[1232b]
d M
z
dt
= M
y '
B
1
M
z
M
0
!
1
[1232c]
In the old CW (continuous wave) spectrometers, one swept either
the frequency
1
or the field
B
1
until the resonance condition was
reached, as discussed above. This was done slowly so as to maintain
steadystate conditions. Under these circumstances, M
x '
, M
y '
and M
z
remained constant in the rotating frame. Therefore, we write:
0=M
y '
(
1
0
)
M
x '
!
2
0=M
x'
(
1
0
)+ M
z
B
1
M
y'
!
2
0= M
y'
B
1
M
z
M
0
!
1
This being three equations in three variables, M
x '
, M
y '
and M
z
, we can
solve for each of the magnetisation components using our matrix
algebra. First, to simplify things a bit we will rewrite our Bloch
equations:
M
x '
+!
2
(
1
0
) M
y '
+0 M
z
=0
!
2
(
1
0
) M
x '
M
y '
+!
2
B
1
M
z
=0
0M
x
' !
1
B
1
M
y '
M
z
=M
0
Here we have multiplied by T1 or T2 as needed to get rid of the
fractions and added 0M
x '
and 0M
x '
for clarity. Also,
1
has been
replaced by
B
fic
as it was defined in equation 1227. It is still
cluttered so let's simplify a bit further by letting:
a=!
2
(
1
0
)
b=!
2
B
1
"=!
1
B
1
The set of equations now looks like:
M
x '
+a M
y '
+0 M
z
=0
a M
x'
M
y '
+b M
z
=0
0M
x
' " M
y '
M
z
=M
0
and when we put them into matrix form:
1 a 0
a 1 b
0 " 1

M
x '
M
y'
M
z

=
0
0
M
0

Recalling the information on solving equations via matrices we
construct the inverse matrix of the coefficients of M, being very
careful about signs of cofactors and transposing to get the adjoint
matrix:
ad#
1 a 0
a 1 b
0 " 1

det
1 a 0
a 1 b
0 " 1

1 a 0
a 1 b
0 " 1

M
x'
M
y '
M
z

=
ad#
1 a 0
a 1 b
0 " 1

det
1 a 0
a 1 b
0 " 1

0
0
M
0

which becomes:
M
x '
M
y '
M
z

=
ad#
1 a 0
a 1 b
0 " 1

det
1 a 0
a 1 b
0 " 1

0
0
M
0

det
1 a 0
a 1 b
0 " 1

=1(1+b")a(a0)
=(b"+1+a
2
)
ad#
1 a 0
a 1 b
0 " 1

=
1+b" a ab
a 1 b
a" " 1+a
2
So we have:
M
x '
M
y '
M
z

=
1+b" a ab
a 1 b
a" " 1+a
2
(b"+1+a
2
)
0
0
M
0

=
M
0
ab
M
0
b
M
0
(1+a
2
)

( b"+1+a
2
)
and we finally arrive at our solutions (after substituting for a, b
and c from our definitions and factoring 1 from the numerator and
denominator):
M
x
' =
M
0
!
2
2
B
1
(
1
0
)
2
!
1
!
2
B
1
2
+1+!
2
2
(
1
0
)
2
M
y
' =
M
0
!
2
B
1
2
!
1
!
2
B
1
2
+1+!
2
2
(
1
0
)
2
M
z
=
M
0
(1+!
2
2
(
1
0
)
2
)
2
!
1
!
2
B
1
2
+1+!
2
2
(
1
0
)
2
It is generally the case that
B
1
is only few milligauss and if T1
and T2 are only a few seconds each:
2
B
1
!
1
!
2
1
and our equations in the xy plane can be approximated:
M
x
' =
M
0
!
2
2
B
1
(
1
0
)
1+!
2
2
(
1
0
)
2
M
y
'=
M
0
!
2
B
1
1+!
2
2
(
1
0
)
2
A plot of M
y '
vs
1
looks like:
This is the Lorenzian or absorbtion line shape. M
x '
vs
1
plots as:
Figure 1219
and is the dispersion line shape.
The Vector Model of NMR Spectroscopy
Strictly speaking this topic is not mathematical as much as it
is pictorial however it follows directly from the development of the
Bloch equations and is very useful in introductory nmr spectroscopy.
The pictures that it provides will help us greatly in understanding
the more obtuse theoretical discourses to follow.
We have spoken of the equilibrium magnetisation and pictured it
as a vector in cartesian space in figure 1212. We have also spoken
of how it is that this vector can move through this cartesian space
via the effect of an applied linearly oscillating magnetic field,
B
1
(figure 1214).
Let's suppose that we have a spin system at equilibrium in an
external magnetic field and we apply a
B
1
field pulse. How can we
picture what will happen given what we have discussed so far? We have
seen that in the rotating frame of reference if the
B
1
frequency is at
or very near
0
, the intrinsic Larmor frequency of the spin, the
external field
B
1
effectively collapses to zero (equation 1228 with
0
=
1
). Thus, what the equilibrium magnetisation 'sees' in the
rotating frame of reference is a static
B
1
field oriented along an
axis in the xy plane:
Figure 1220
What will happen? The equilibrium magnetisation will precess about
B
1
of course.
Figure 1221
x
y
z
M
0
B
1
Figure 1222
x
y
z
B
1
In Fourier Transform nmr spectroscopy, turning on the
B
1
field for
enough time that the magnetisation rotates by 90 degrees into the xy
plane is commonly referred to as issuing a 90 degree pulse.
Similarly, a 180 degree pulse effects a rotation of the magnetisation
by 180 degrees.
When we turn off the
B
1
field what happens? If the magnetisation
has been rotated into the xy plane it will now precess about
B
fic
,
which will be zero if the pulse is 'on resonance' and nonzero
otherwise. 'Onresonance' generally means
0
=
1
in equation 1228. For
a set of spins with differing chemical shift frequencies only one
spin can experience an onresonance pulse while the others will
experience varying degrees of
B
fic
. It is easiest to begin describing
pulse sequences with onresonance pulses. So, we have a spin whose
magnetisation is in the xy plane as a result of an onresonance 90
degree pulse. This being the case, in the rotating frame there will
be no apparent chemical shift evolution since the Larmor frequency of
the spin is the same as the rotating frame frequency. It will be
motionless.
Scalar coupling evolution can be represented vectorially as a
splitting of the vector into two or more vectors with differing
Figure 1223
x
y
z
B
1
rotational frequencies in the rotating frame. If we imagine for
convenience an onresonance 90 degree pulse issued to a spin that is
split into a doublet our vector model will have the vector in the xy
plane split into two 'sub vectors', one rotating clockwise in the
rotating frame and one rotating counterclockwise. Why is this? Well,
an onresonance pulse is issued at the chemical shift frequency of
the spin. Thus the 'zero' frequency is the chemical shift frequency;
that is, in the rotating frame the chemical shift of the spin appears
to be zero. However, for a doublet in an nmr spectrum the chemical
shift is halfway between the two peaks observed. Thus one peak is
slightly behind the rotating frame frequency and one is slightly
ahead by the same amount. Therefore, in the rotating frame we picture
two counterrotating vectors:
Note that we have changed our perspective here for convenience. We
are now looking down from 'above' the xy plane. The coupling
constant, usually measured in hertz, is the frequency difference
between the peaks of the multiplet in the spectrum. For a doublet
this is J Hz and in our picture, one vector rotates with relative
frequency +J/2 Hz and one with relative frequency J/2 Hz. Why J/2?
Remember that we are thinking in the rotating frame of reference and
that the chemical shift frequency is zero. Since the frequency
difference between the doublet peaks is J Hz, one of the two doublet
peaks will rotate at +J/2 Hz and the other at J/2 Hz relative to the
chemical shift frequency.
Now, suppose we wait for a period of time after the
B
1
field is
turned off. Furthermore, let's assume an onresonance pulse for
simplicity and clarity and a doublet with coupling constant J Hz. If
the time period is 1/(2J) seconds where will the doublet vectors be?
Figure 1224
x
y
We need to calculate how far the vector will have rotated:
=t
=2$
1
2J
=
This gives the angle between the two counterrotating vectors. Half
of this then will be the angle that one of the vectors will have
rotated through:
=t
= $
1
2J
=
2
Thus, one vector which is rotating clockwise will rotate +90 degrees
and the other 90 degrees:
We can apply these simple principles to several pulse sequences. The
Jmodulation experiment consists of pulses on two channels, usually
1
H and
13
C:
Figure 1225
x
y
The effect of the
1
H decoupler is to collapse multiplets into
singlets. In other words, multiplet vectors collapse to a single
vector located at the chemical shift frequency. So, in this pulse
sequence there is coupling evolution during the first delay period of
1/J seconds but not during the second delay period. How is this
useful? During the first delay period the two counterrotating
vectors of the doublet will each rotate by 180 degrees and will be
colinear along (say) the yaxis. The 180 degree pulse on
13
C
rotates them back to where they started. The decoupler collapses them
to a single vector which will now exhibit only chemical shift
evolution. Assuming onresonance pulses, this will be zero so that
the vector is motionless in the rotating frame during the second
delay period. Acquisition then gives a spectrum with a (decoupled)
13
C peak in it.
The interesting part of all of this is what happens when we
2
H
1
C
13
decoupler
acquisition
1
J
1
J
Figure 1226
1
J
1
J
x
{ H
1
}
consider now a triplet, again with coupling constant J Hz. Still
assuming an onresonance pulse for convenience, the vector
representing the center peak will be motionless in the rotating frame
since it is also at the chemical shift of the multiplet and the other
two vectors will rotate at +J Hz and J Hz with respect to the
chemical shift frequency. This is just twice that of the doublet so
each of the 'outer' vectors will rotate twice as far in 1/J seconds.
Using our APT pulse sequence analysis from above the vector diagrams
will look like:
The vector at acquisition time is now pointed 180 degrees away from
where the double vector was. This will result in a peak in the
13
C
spectrum that is 180 degrees out of phase with the doublet peak. The
APT experiment is a very useful way to ferret out the multiplicity of
13
C peaks.
The vector model is very useful for introducing the analysis of
pulse sequences but there comes a point at which it breaks down.
Specifically, when multiple quantum coherence is generated it is not
possible to follow the evolution of the magnetisation using the
simple vector model. Fear not however. There are other ways to do so
and the vectorpicture will be useful in introducing them.
Figure 1227
1
J
1
J
x
{ H
1
}
Prolems
References
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2. H.C. Torrey, Phys. Rev., 76, 10591068, (1949).
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(1994).
4. P.K. Madhu and A. Kumar, J. Magn. Res. A, 114, 201212, (1995).
5. P.K. Madhu and A. Kumar, Concepts in Magnetic Resonance, 9, 1
12, (1997).
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