Escolar Documentos
Profissional Documentos
Cultura Documentos
Chapter 1
NMR Theory
In order to understand NMR, one needs to have a basic understanding of the principles
behind how an NMR signal is generated and manipulated. This chapter briefly covers
NMR fundamentals, from the origins of the signal, to the acquisition and processing of
the signal. There are numerous texts available which give a more detailed discussion of
these principles. For the purposes of this dissertation, only the relevant terms will be
introduced and discussed. More intricate details of the NMR phenomena and terms
relating to it can be found in texts by Callaghan (1991), Abragam (1961), and Morris
(1985).
r
In classical electrodynamics, the magnetic field, H , induced by a current, I, in an n-turn
r 2πnI
H= . [1.1.1]
r
NMR THEORY 2
The above equation holds for a field produced via electrical induction and can be
modified to include the effects of the sample’s bulk susceptibility, χ m , to give the
r r
B = µ 0 (1 + χ m ) H [1.1.2]
where µ 0 is the permeability constant of free space. A careful study of Eq. [1.1.2] shows
that depending on the susceptibility of the sample, the field strength within the sample
r
can be greater than the applied field. Many authors choose to call H the magnetic field
r r
and B the flux density. But in classical magneto-statics, B is indisputably the
r
fundamental quantity so, in this work, B will be referred to as the magnetic field.
r
A fundamental tenet of quantum mechanics states that the angular momentum ( P ) of a
r
P = h I ( I + 1) [1.2.1]
NMR THEORY 3
momentum vector is quantized. This implies that the z-component of the angular
where mi is referred to as the directional (or magnetic) spin number. For a spin- 12
r r 3
nucleus, the possible orientations of P are represented in Fig. 1.2.1, where P = h,
2
h −1 Pz
Pz = ± , and θ = cos r .
2 P
r
The nuclear dipole moment, µ , is related to the nuclear spin angular momentum by the
r r
µ = γP [1.2.3]
values.
given by:
r r mI
E = µ • B0 = − µB0 cos(θ ) = µB0 1
. [1.2.4]
[I (I + 1)] 2
r
For a spin- 12 system, there are only two possible orientations of µ , hence the z-
component of the nuclear dipole moment, µ Z , can either be parallel or anti-parallel with
r
respect to B0 (Fig. 1.2.2). The energy associated with each orientation is given by
NMR THEORY 5
γhB0
E = ± µ z B0 = ± . [1.2.5]
2
γhB 0 γhB 0 γ
∆E = −− = γhB 0 = hB 0 . [1.2.6]
2 2 2π
∆E = E a − E b = h ν , [1.2.7]
γ
hB0 = hν . [1.2.8]
2π
ω = 2πν = γB 0 . [1.2.9]
Eq. [1.2.9] is the quantum mechanical expression for the resonance condition and
between energy levels, is directly proportional to the magnetic field strength, B0 , by the
gyromagnetic ratio, γ .
static magnetic field. However, in NMR, the signal arises from the vector sum of the
r
individual µ . This distribution of individual magnetic moments amongst the various
EI
−
NI = e kT
[1.2.10]
J
where k is the Boltzmann constant ( 1.38 × 10 − 23 ), and N I is the number of spins at
K
energy E I and temperature T (in Kelvin). Since only population differences between
energy states can be detected by NMR, and the population difference can be represented
as
∆E γhB0
∆n =
2kT
∑N I =
2kT
∑N I , [1.2.11]
1 γ 2 h 2 B0
M0 =
2
γh (∆n ) =
4kT
∑N I [1.2.12]
NMR THEORY 7
r
Another useful way to visualize the behavior of the nucleus is to consider µ classically
r r
as a small magnet. If µ is inclined at an angle with respect to B0 (Fig. 1.2.2), a torque is
r r r
exerted on µ which causes it to precess about B0 . The precessional behavior of µ is
r
dµ r r
= γµ × B 0 . [1.2.13]
dt
r
Since the net magnetization vector is the sum of the individual spins, the behavior of M 0
r
dµ r r
(
∑ dt = ∑ γµ × B0 ) [1.2.14]
or
r r
dM 0 dµ r r r r
dt
=∑
dt
( )
= ∑ γµ × B0 = γM 0 × B0 . [1.2.15]
The solution (Callaghan, 1991; Halliday and Resnick, 1988) to Eq. [1.2.15] corresponds
r
to a precession of the magnetization about the B0 field at a rate of
NMR THEORY 8
ω 0 = γB 0 . [1.2.16]
Eq. [1.2.16] is known as the Larmor equation and is the fundamental equation describing
the static magnetic field, it is convenient to consider a rotating frame of reference equal to
that of the Larmor frequency of the nuclei under observation. In this reference frame, the
precessing magnetization appears stationary and allows for simpler visualization of the
NMR THEORY 9
r r
dM r r ω
= γM × B 0 + . [1.3.1]
dt rotating γ
r
ω
where represents the term from the rotating frame of reference. It can be seen from
γ
r
this equation that an exact cancellation of the influence of B 0 can be achieved by setting
r
ω r
− = B0 , [1.3.2]
γ
r
a condition which is satisfied when the frequency of the rotating frame of reference ( ω )
is equal to that of the Larmor frequency. Since the Larmor equation describes a
precessional dependence of the net magnetization vector on the static magnetic field, the
r
with an oscillating radiofrequency (RF) magnetic field, B1 , Eq. [1.3.1] can be modified to
r
dM r r ωr r
= γM × B0 + + B1 . [1.3.3]
dt rotating γ
NMR THEORY 10
Now if the frequency of the rotating frame of reference is set exactly equal to the Larmor
frequency (Eq. [1.3.2]), the static term and the precessional term cancel and Eq. [1.3.3]
simplifies to:
r
dM r r
= γM × B1 . [1.3.4]
dt rotating
Thus, from a frame of reference that is rotating at the Larmor frequency, an oscillating RF
r r
field of exactly the same frequency in a plane perpendicular to B0 produces a static B1
r
field in the rotating frame of reference that is orthonormal to B0 . The spins will precess
r
about B1 at a frequency given by
ω 1 = −γB1 . [1.3.5]
If the duration of the oscillating RF field can be controlled, the precessional or tip angle
of the net magnetization around the orthonormal axis can be calculated using
where t tip is the duration of the oscillating RF field and θ tip is the tip or flip angle. By
controlling the duration ( t tip ) and/or the amplitude ( B1 ) of the RF excitation pulse, an
1 1
amplitude (Amps)
amplitude (Amps)
0 0
-1
-1
time tim e
Fig. 1.4.1. The free-induction decay (FID). The FID (left) shows the time-
varying current induced into a resonant circuit from the magnetization
precessing in the transverse plane. The sinusoidal behavior of the FID is
enveloped in a decaying exponential characterized by a time constant, T 2* . The
same FID as seen from the rotating frame of reference with a frequency exactly
equal to that of the Larmor frequency (right) exhibits the behavior of a
decaying exponential with no oscillating component.
Following RF excitation, the net magnetization vector precesses in the transverse plane
and acts as a time-varying magnetic field oscillating at the Larmor frequency. According
to Faraday’s Law, this time-varying magnetic field can induce a current into a resonant
circuit tuned to the oscillating frequency. This detected signal is referred to as the free-
Two important characteristics of the FID are the frequency component and the component
of decay. Since the excited spins precess at their respective Larmor frequencies, and the
system is observed from the rotating frame of reference, the frequency components within
the FID are simply the differences between the rotating frame frequency and the Larmor
frequencies. The exponential decay constant is a measure of how quickly the observed
Given this, the behavior of the magnitude of the transverse magnetization (and hence the
t
−
T2*
M xy = M 0 e [1.4.2]
where M xy is the observed signal intensity of the FID at time, t, and M 0 is the initial
respective Larmor frequency components, another mode with which the signal can be
visualized is in the frequency domain. Although the information contained in the time
NMR THEORY 13
domain signal is identical to that of the frequency domain, the extraction of complex
The Fourier relation between the time domain signal, f(t), and its frequency domain
∫ f (t )e
− iωt
F (ω ) = dt [1.5.1]
−∞
∞
1
∫ F (ω )e
iωt
f (t ) = dω [1.5.2]
2π −∞
for the inverse of the Fourier transform (IFT). Since the FT and the IFT are merely
domain, and vice versa. This is known as the convolution theorem (Peebles, 1987).
Several important Fourier pairs commonly used in NMR are shown in Fig. 1.5.1.
t
−
T2*
Since the FID takes the shape of sin (ω 0 )e , it is important to know the frequency
domain representation of this exponentially decaying sine wave. The FT of the FID
NMR THEORY 14
height of
1
f FWHM = [1.5.3]
πT2*
sin( x)
symmetrically disposed about the origin in the frequency domain corresponds to a
x
function (also called a sinc function) in the time domain. Recalling the convolution
theorem, we see that enveloping a sine wave with a sinc function (multiplication of a sinc
function and a sine wave) acts to shift the rectangular wave in the frequency domain
1.2
Amplitude (Arbitrary
1.2
Units)
0 0.8
0.4
0
-1.2 -0.4
ω0)
ω0
sin(ω0 δ(ω−ω0)
time frequency
Amplitude (Arbitrary
1
Units)
0
exp(-t/T2*) Lorentzian
time frequency
(Arbitrary Units)
Amplitude
Amplitude (Arbitrary
Amplitude (Arbitrary
Units)
Units)
Time ω 0
ω0t)
exp(-t/T2*)sin(ω F req u en cy
Fig. 1.5.2. The FID and the Fourier transform (FT) of the FID. The line
shape that results from the FT of the FID is characterized by a Lorentzian.
The FID displays information from the time domain while the FT of the FID
displays frequency components. In this example, the center frequency of the
Lorentzian is the frequency of the enveloped sine wave, and the full width at
1
half-maximum height (FWHM) of the Lorentzian is proportional to .
πT2*
f0
sin(f0)
Fig. 1.5.3. Sinc and rectangular wave Fourier pair. Excitation in the time
domain via a sinc functional form is analogous to excitation of a rectangular
wave in the frequency domain. Enveloping a sine wave with frequency, f0, in
a sinc envelope in the time domain shifts the rectangular wave in the
frequency domain to a position centered around f0.
NMR THEORY 17
relaxation processes. Here the processes are briefly discussed as well as methods for
measuring the associated relaxation time constants. A more detailed explanation of these
(1961).
Recalling that the NMR signal is generated from the vector sum of parallel and anti-
parallel spins (Section 1.2, Fig. 1.2.3), we see that at Boltzmann equilibrium, more spins
are aligned parallel to the external magnetic field than anti-parallel. A 180° inversion
pulse deposits energy into the system causing a transition of spins from the lower energy
state, E1, to the higher energy state, E2 (Fig. 1.6.1.1). Immediately following this
inversion pulse, the spin system begins to evolve back to thermal equilibrium by releasing
its deposited energy to the surroundings (the “lattice”). This spin-lattice relaxation is
governed by a time constant, T1 , and the differential equation describing this phenomena
dM z 1
= − (M z − M 0 ) . [1.6.1.1]
dt T1
NMR THEORY 18
Since the spins are randomly ordered around the z-axis, the x- and y-components of M
cancel and MZ is the only nonzero component. Therefore, when spins are inverted by a
180º RF pulse, only the magnitude of MZ is affected. Similarly, when the spins relax back
Fig. 1.6.1.1. Inversion of spins upon application of a 180° pulse. Absorption of energy
causes an excitation of spins from the lower energy state, E1, to the higher energy state,
E2. Once excited, these excited spins relax back to ground state (E1) as energy is
released to the lattice. Since only the z-component of relaxation is affected by T1
relaxation, the spin states in E1 and E2 represent the parallel and anti-parallel µZ.
−
t
M z (t ) = M 0 1 − e 1T [1.6.1.2]
NMR THEORY 19
for the case where a 90° RF pulse is applied. In an NMR experiment, the time t is usually
referred to as the repetition time (TR, the time at which the spins are successively excited
One way to measure the T1-relaxation time constant is by using a pulse sequence known
pulse is applied to the spins to invert the net magnetization vector. Following inversion,
as the spins recovers to Boltzmann equilibrium, a 90° RF pulse is applied at various time
intervals (TI), thus tipping the magnetization into the transverse plane where the signal
can be measured. The measured signal will be dependent on TI (Fig. 1.6.1.3) according
to:
−
TI
M xy = M 0 1 − 2e T1 . [1.6.1.3]
NMR THEORY 20
If the inversion pulse is not exactly 180°, then the above equation will take on the form
−
TI
M xy
= A 1 − Be T1 [1.6.1.4]
where A is some fraction of M0 and B (a number less than two) gives some indication of
the inversion efficiency. The measured data can then be fitted for T1 using Eq. [1.6.1.4].
I n v e r s io n R e c o v e r y C u r v e
Signal Amplitude
T im e (t)
While the T1 relaxation-time constant describes the recovery of the spin system to the
how quickly the observable signal disappears. The observable signal is comprised of the
vector sum of individual spins, and it is the coherent precession of these individual spins
The resonant condition between spins of the same frequency allows for energy exchange
between these spins and is responsible for spin-spin relaxation. Intra- and intermolecular
interactions cause the local magnetic field around the spins to fluctuate causing slight
of phase coherence in the net transverse magnetization as the spins exchange energy and
There are several possible causes for a loss of phase coherence. The modulation of the
local magnetic fields due to molecular interactions (T2) is one of the causes, but magnetic
field inhomogeneities and other factors can also contribute to the dephasing of the
experience slightly different B 0 fields and precess at different Larmor frequencies, thus
causing a loss of phase coherence. For this reason, the attenuation of the signal (or FID)
NMR THEORY 22
is not only affected by the inherent T2, but also diffusion, magnetic susceptibility, and
inhomogeneity effects. All of these factors contribute to a time constant known as T2*
according to
1 1 1 1 1
*
= + + + . [1.6.2.1]
T2 T2intrinsic T2diffusion T2susceptibility T2inhomogeneities
For the purposes of many NMR experiments, it would be advantageous to recover the
signal loss due to susceptibility and inhomogeneity effects. A method to reverse the time
evolution of spins was presented in a seminal paper by Erwin Hahn (1950). It was shown
that a 180° RF pulse applied τ seconds after an initial 90° excitation RF pulse would
cause the phase reversal necessary for refocusing the transverse magnetization at time 2τ
(Figs. 1.6.2.1 and 1.6.2.2). The refocused echo is known as the Hahn spin echo, and the
attenuation of the signal at 2τ becomes a function only of the intrinsic T2 relaxation time
of the nuclei. The equation of motion for the transverse component of magnetization,
Fig. 1.6.2.2. Spin behavior during Hahn spin echo pulse sequence. The initial 90°
excitation pulse tips the net magnetization into the transverse plane. During the time
interval between the 90° and 180° RF pulse (τ), these spins dephase due to magnetic field
inhomogeneity and other effects. A 180° RF pulse flips the spins around an axis causing a
phase reversal. The spins refocus at time τ after the 180° RF pulse and the echo that forms
is known as the Hahn spin echo.
dM xy 1
=− M xy [1.6.2.2]
dt T2
t
−
T2
M xy = M 0 e [1.6.2.3]
NMR THEORY 24
where t is the echo time (t = 2τ), or the time between the first RF excitation and