Nuclear Magnetic Resonance

Giovanni Pinuellas
13 December 2010

Abstract
In this lab we observe nuclear magetic resonance phenomenon in glyc-
erin, water and teflon. We performed two experiments. The continuous
wave NMR experiment was used to determine the resonance frequency of
our samples as well as the magnitude of the magnetic field of our perma-
nent magnet. The pulsed NMR expeiment was used to observe spin echo
phenomenon and determine the relaxation time T2.

1 General Theory
Nuclear magnetic resonance (NMR) is the phenomenon that happens when mag-
netic nuclei are immersed in a static magnetic field and then exposed to another
oscillating magnetic field. Magneic atomic nuclei have a magnetic moment, µ,
that is proportional to the angular momentum and a constant of proportionality
known as the gyromagnetic ratio, γ. Usually we consider a frame of reference
along the z-axis (the static field is orientied along the z-axis), so that

µ = γSz

where Sz is z-component of the angular momentum vector S. For spin 1/2 par-
ticles (such as the protons we will be observing in this experiment) Sz = m� =
± 12 �, since m takes the values +1/2 (spin down) or -1/2 (spin up). At a zero
external field the energies of these magentic moments are degenerate, but when
placed in a magnetic field these two states decouple. The interaction between
the magnetic moment in a magnetic field results in a magnetic interaction known
as the Zeeman interaction. The interaction energy of the magnetic dipole µ in
a magnetic field Bo is defined by the hamiltonian

H = −µ · Bo = −γm� · Bo

and since we orient Bo in the z-direction,

H = −µBo = −γm�Bo

and therefore the separation of energies between Zeeman splittings is always

γ�Bo for whatever m.

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 In the Schrödinger picture
∂
i� |Ψ(t) >= H|Ψ(t) >
∂t
and if H is contant with time then the Schrödinger equation yields the result

|Ψ(t) >= U (t)|Ψ(0) >

where
U (t) = exp (−iHt/�) = exp (iγmBo t)
is the evolution operator, which is identical to a clockwise rotation of the state
about the z-axis by an angle γBo t. This has the effect that all states will precess
at the Larmor frequency ωo given by
υo = γBo.
This precession is called Larmor precession, and is anologous to the classical
picture as a magnetized compass needle experiencing a torque by its intercation
between the north and south poles of a magnet. The magnetic field of this
magnet will interact with the compass needle (the magnetic moment of the
nucleus) to create equal and opposite forces at its ends that creates the torque
τ = γM × B
and thus begings to rotate. The solution to this equation when B =Bo ẑ also
corresponds to a Larmor precession of the magnetization about the field at the
rate υo = γBo .
We can define an ensemble magnetization M that is the defined as the net
magnetization of individual magnetic moments. In this model the macroscopic
angular momentum vector is M/γ, and equating the torque to the rate of change
of angular momentum we have
dM
= γM × B. (1)
dt
In the equilibrium state the ensemble magnetization lies along the direction
of the static field Bo . We denote this equilibrium magnetization as Mo . The
z-component of M is called the longitudinal magnetization, Mz , and in this
configuration M =Mz = Mo . The transverse magnetizations here, Mx and My
are 0.
We apply an external RF field to disturb the spin state from its thermal
equilibrium state. This has the effect of tilting M to the transverse plane by
exposing the spin states to an energy of a frequency equal to the energy differ-
ence between the states. In time this equilibrium is restored by a spin-lattice
relaxation process, which involves the exchange of energy between the spins and
the surrounding thermal reservoir (the ’lattice’) which it is in equilibrium. This
process is governed by the equation
dMz Mz − Mo
=− (2)
dt T1

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with solution
Mz = Mo (1 − 2 exp (−t/T1 )). (3)
Here T1 is called the spin-lattice (or longitudinal) relaxation time. It is the
time constant which describes how Mz returns to its equilibrium value Mo , as
seen in (3). As mentioned, it is mainly due to the thermal interactions of the spin
states. Additionally, with the introduction of paramagnetic ions such as M++
the T1 time is significantly decreased as the stronger magnetic moments restore
the ensemble magnetization to its equilibrium state faster. This is because the
width of the voltage response versus time plot has a 1/T1 relationship.
We can apply a “π/2” pulse to our spin system to completely shift the ensem-
ble magnetization M to the xy plane (transverse magnetization). This rotates
the magnetization 90º. With M = Mx + My , the transverse magnetization will
begin to precess around the z-axis with frequency υo . But here the inevitable
inhomogeneity of the applied magnetic field over the dimensions of the ensem-
ble will disrupt the Larmor frequencies of all the spins. This will essentially
cause the spins to dephase as individual spins will precess at different rates,
with differing rates. Eventually in time the spins can completely decay to yield
Mxy = 0. This decay is called the called spin-spin relaxation and it is described
by
dMx,y −Mx,y
= (4)
dt T2
with solution
Mx,y = Mx,y (0) exp (−t/T2 ) (5)
where Mx,y (0) is the initial transverse magnetization immediately after the π/2
pulse is applied.
Spin-spin relaxation is governed by T2 , the spin-spin relaxation time. T2
is the time constant that describes the transverse magnetization returning to
thermal equilibrium among themselves. It is also called the dephasing time,
which is the time required for Mx,y to decay to 0. For T2 processes, spin-lattice
effects are still present, but the effect of phase decoherence between nuclear spin
states dominates. This results in T2 ≤ T1 .
It is convinient to define a rotating plane S � which rotates about the longi-
tudinal axis at the Larmor frequency υo . The Z axis remains unchanged but we
distinguish the rotating X and Y axes by X’ and Y’. Correcting (1) using (2),
and (4) in this rotating frame yields the set of relationships known as the Bloch
equations:
dMx Mx
= γ(M × B)x −
dt T2
dMy My
= γ(M × B)y −
dt T2
dMz Mo − Mz
= γ(M × B)z + .
dt T1

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 Without damping (none of the T1 or T2 terms) the Bloch equations are just
as in (1):
dMx,y,z
= γ(M × B)x,y,z .
dt
Magnetization can be measured by free nuclear induction created by the
precession of the ensemble magnetization. Surrounding our sample is a receiver
coil that when precession occurs, a voltage is induced in the coil. This voltage
is defined by V = − dφdt , or the negative of the flux through the coil. Depending
on the degree saturation, we can observe either an adiabatic (slow passage)
or a non-adiabatic (fast passage) resonance pattern based on the amount of
paramagnetic ions in our samples. Adiabatic passage corresponds to a smaller
T1 , while non-adiabatic passage corresponds to a bigger T1 .
We can measure this induced voltage with our electronics. Additionally, we
can meausure the spin-spin relaxation time T2 by reproducing a process known
as spin echo. After an RF pulse of π/2 is applied, the transverse magnetization
dephases. Here we can say that the spins in frame S � rotating with Larmor
frequency υ = υo + u have precessed by an angle ut. We can then apply an
additional π pulse which corresponds to a rotation of 180º about X � of the
plane S � . At the end of the pulse the spins of frequency υo + u will have a phase
−u(t + τ ) with respect to X � and thus at a time 2(t + τ ) they will be aligned
again. Therefore the transverse magnetization will add constructively to the
value equal to the one immediately following the first pulse.
Physically this π/2 and π pulse procedure has the effect of reversing all spin
precessions. This results in the spins recohering as the slower spins are now in
front and the faster ones in the back. The faster precessions will recombine to
rephase to Mx,y (0), then dephase again to 0. Half of this time is equivalent to
the spin-spin relaxation time T2 .

2 The Continous Wave NMR Experiment

2.1 Apparatus and Theory
We first investigate NMR with the continous wave (CW) NMR experiment. Here
we examine protons and F19 in a static magnetic field provided by a permanent
magnet of Bo ≈ 3.9 kG (with the purpose of measuring the magnetic field
Bo as precicely as we can with this procedure). We observe NMR phenomena
by using a continuous RF field tuned to resonance and modulating the static
field sinusoidally around resonance. This method probes the induced voltage
response at a fixed resonance with varying magnetic field. Alternatively, we
could have left the magnetic field fixed and varied the RF frequency.
We apply the RF field B1 perpendicularly to the static field. This field is
provided by a tunable RF oscillator coil.√ The frequency is determined by an
inductor and a capacitor, where υo = 1/ LC. One variable capacitor tunes the
frequency. This coil in enclosed in a black box we call the NMR head. The RF
field can be set to either absorption or dispersion by adjusting a copper disk

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on the cavity of the NMR head. This changes the direction of B1 relative to
the receiver coil, or in other words, the phase of the leakage voltage into the
receiver coil. With this we can view an absorption resonance pattern where we
modulate across the magnetic field at almost an angle of the field B1 perpen-
dicular to the direction of the static field Bo . The resonance pattern should be
very symmetrical about Bo , as we see in their respective figures. In dispersion,
because this angle is off, the leakage voltage is dependant on the frequency and
thus we see a dispersion pattern. The amplitude of B1 is controlled by the DC
supply voltage to the oscillator.
For the samples we use glycerin, H2 O+MnCl2 4H2 O at a range of molarities,
and F19 in the form of teflon rods. We place the tubes inside the NMR head
where they are wrapped around receiver coils to pick up the induced voltage
from the precessing ensemble moment. The NMR head is placed between the
static magnetic field of a permament magnet. This static field is modulated at
60Hz by an oscillating field Bmod by two small coils located on the top and the
bottom of the NMR head.
With the RF field tuned to the Larmor frequency corresponding to υo = γBo ,
the RF signal is absorbed by the spins and it produces the precessing ensemble
moment cause by the shifting to the transverse plane. This precession induces
an emf in the receiver coils, which when plotted against the input modulation
results in the resonance patterns in an oscilloscope or with a LabView program
on the computer.
Further investigation involved fine-tuning the NMR resonance by leaving
the RF frequency constant and applying another small field B2 by using a
wave generator to drive another set of wire coils. We use a lock-in amplifier
to sweep slowly across a range of magnetic fields. We set this modulation
to be very small and record the derivative of the output signal. The lock-in
amplifier is used to detect and measure very small AC signals by a phase-
sensitive detection technique that singles out the component of the signal at a
very specific reference frequency and phase. Noise signals at frequencies other
than the reference frequency (here 60 Hz) are ignored. This is accomplished by
muliplying the signal by a pure sine wave at the reference frequency. Because
sine waves of different frequencies are orthagonal, when integrating over a period
all other signals are filtered. The output is recorded in a strip chart using the
LabView program.

2.2 Results
For glycerin we find the resonance frequency to be within the range of 16.525±0.001
MHz. This error is due to the systematic error due to the accuracy of the fre-
quency counter. This yields a magnetic field Bo = 3881.8±0.0046 gauss. The
following is the calibrated resonance pattern for glycerin non-adiabatic (fast)
passage absorption. This results because the concentration of paramagnetic
ions is low. We can clearly see characteristc “wiggles” which indicate the inho-
mogeneity of the magnetic field. We can estimate the inhomogeneity from the
damping rate of these wiggles, which we detremine to be 1.50±0.25 gauss.

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 We replace the glycerin sample with a 0.01M Mn++ solution in water. Here
the signal is also that of non-adiabatic absorption, where we can also clearly see
the characteristic wiggles.

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 With the 1M Mn++ sample we observe both absorption and dispersion res-
onance patterns, but this time adiabatically (slow passage). This is because of
its high concentration of paramagnetic ions decreased T1 , which corresponds to
a slow passage. The two plots in figure 1 show these patterns.
We also observed the resonance patterns of T19 nuclei in a teflon rod. Here
we measured a resonance of 15.538±0.001 MHz. Here the absorption peak is
less pronounced than the protons’ because of the larger mass of the flourine
nucleus. The patterns of both absorption and dispersion are shown in figure 2.
Measuring both resonance frequencies of H1 and F19 under identical conditions
we can determine the ratio of their resonance frequencies. We find that the
ratio of F19 to H1 is 0.940±9.451×10−6 . This is also the ratio of their magnetic
moments.
We then observe sequence of absorption lock-in trace from the computer for
molarities M=0.03, 0.1, 0.3, 1, 3.3 Molar Mn++ . These are shown in figures 3,
4, 5, 6 and 7, respectively. As we can observe, the line widths slightly decrease
with increased molarity. This is to be expected, as an increased concentration of
protons will decrease the T1 relaxation time as the stronger magnetic moments
restore the ensemble magnetization to its equilibrium state faster.

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Figure 1: Resonance patterns for 1M++

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Figure 2: Resonance patterns for F19

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Figure 3: Strip chart for 0.03M Mn++

Figure 4: Strip chart for 0.1M Mn++

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Figure 5: Strip chart for 0.3M Mn++

Figure 6: Strip chart for 1M Mn++

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Figure 7: Strip chart for 3.3M Mn++

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3 The Pulsed NMR Experiment
3.1 Apparatus and Theory
In The CW NMR experiment we observed nuclear resonance of the ensemble
magnetization of our samples in a static magnetic field by modulating this field
at 60 Hz while applying a continuous RF field perpendicular to the static field.
The alternative in the pulsed NMR experiment is to instead apply a short intense
RF pulse and observe the signal after the pulse is removed. This has the same
effect as like the ringing of a bell. We will observe the ringing down of the signal
after the pulse is applied.
We apply an RF pulse at near the Larmor precession of the spins using a CW
RF oscillator modulated by a DG535 pulse generator. The duration of the pulse
is calibrated by the pulse generator to correspond to a 90º (π/2) rotation. This
is achieved by setting the digital delay settings on the DG535 to the time that
it takes to translate the ensemble magnetization from the longitudinal plane
to the transverse plane, which in turn is figured out by searching for the time
that corresponds to the maximum voltage response in our detector coil due to
nuclear induction by the precessing spins.
Once they’re down in the transverse plane we turn off the excitation pulse.
The spins precess at the Larmor frequency but after a time the spins will dephase
because of field inhomogeneities. This is the free induction decay. This causes
the signal to decay as the spins dephase to form a “pancake” that makes Mxy = 0.
This dephasing can be reversed by applying a π pulse that reverses the spins
and recoheres Mxy . This pulse is applied just by extending the duration of
the second pulse to double the time of the first pulse. Since the first pulse
corresponded to a π/2 pulse, this pulse will correctly correspond to a π pulse.
If we apply our second pulse at time t then the echo will occur at time 2t. T2
can be measured by the spin echo response. Since this spin echo recoheres then
decays again with a maximum amplitude identical to the first free induction
decay response, half the time of the duration of the spin echo is equal to the
spin-spin relaxation (or dephase) time T2 .
The NMR head for this experiment is replaced by a smaller one with a
single receiver coil. This head is placed inbetween the permanent magnet lined
up at the center of the magner where the static field is most homogeneous. The
RF pulses to excite the system are produced by the CW RF oscillator which
produces continous wave RF voltage at close to the Larmor frequency. We
gate this CW RF oscillator into brief pulses by a pulse genetator and a mixer.
The output of the mixer is a choped section of the square wave outputed by
the pulse generator and the RF voltage. This pulse is then amplified by an
RF power amplifier and then sent to matching capacitors and then to an RF
coil that is used to excite the spins. The precessing magnetization is detected
by the receiver coils and sent through another amplifier and then to a digital
oscilloscope and to the computer where we can actually analyze our signals.

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 Figure 8: Spin echo effect of glycerin

3.2 Results
We found that for glycerin the best duration for a π/2 pulse is 80µs and 3ms
later a π pulse of 160µs. Free induction decay is seen only when we are a little off
the resonance frequency. When we are at the resonance frequency we only see
the envelope of the decay. The next figure shows the spin echo effect on glycerin.
The large spikes are the RF pulses overloading our detectors and their responses
are immediately after. We see our first pulse occur at the 5ms mark followed
by the free induction decay. The second pulse is applied 3ms later at 8ms and
the spin echo is observed at 11ms. Our estimation of T2 is 0.30ms±0.02ms.

4 Conclusion
Traditionally T2 is also measured by applying a Fourier transform to the spin
echo. But our Fourier transform was incoherent because we took our signal
exactly at resonance, producing no wiggles.
Additionally, T1 could have been measured by applying three succesive π/2
pulses. We first apply a π/2 pulse that rotates the magnetization to the trans-
verse plane. Another π/2 rotattion rotates the decayed signal back to the Z
axis, then another π/2 pulse is applied to measure magnetization at time t. If
we measure Mz at different t we can use (3) to calculate T1 . Unfortunately this

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cannot be measured as we can only apply two RF pulses at a time.
Other interesting measurements could be to measure the decay of the spin
echo. In the spin echo procedure we can continue to reapply π pulses to con-
tinue to recohere the phases of the spins. Due to other inhomogeneities in the
environment we will find that the transverse magnetization will not recohere to
a magnitude idential to the last one. This decay of spin echo signals also cannot
be measured by the current NMR setup.

5 References
[1] Paul T. Callaghan. “Principles of Nuclear Magnetic Resonance Microscopy.”
1991 Oxford Science Publications.
[2] A. Abragam. “Principles of Nuclear Magnetism.” 1961 Oxford University
Press.
[3] Felix Bloch. “Nuclear Magnetism.” American Scientists: Vol. 43, No. 1, Jan
1955, pp. 48-62.
[4] Felix Bloch. "Nuclear Induction.” Physical Review 70, 460. No 7 and 8,
(1946).

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