NUCLEAR MAGNETIC RESONANCE

INTRODUCTION

Nuclear Magnetic Resonance (NMR) provides an important probe of the microscopic en-
vironment in solids and liquids. NMR, as a probe of condensed systems, has become an
essential tool in many disciplines, such as physics, chemistry, biology, etc. NMR methods
have also become important in areas such as medicine, where they are used as a diagnostic
tool. The importance of NMR, both as one of the most fundamental examples of resonance
phenomena and as a technologically important tool, makes it an ideal experiment for this
laboratory. [1–5]

NMR operates by observing the absorption or emission of power as transitions are induced
between the nuclear energy levels. Normally, the energy levels are nearly degenerate, making
this a very difficult task. However, application of an external magnetic field can split the
energy nuclear energy levels. Transitions between the nuclear energy levels can then be
induced by an oscillating magnetic field, usually in the radio frequency (RF) range. The
frequency where absorption or emission of power occurs corresponds to a matching of the
energy of the incident radiation to the energy level splitting. These transitions can then
be observed experimentally through their absorption and emission of radiation. Thanks to
the Correspondence Principle, NMR has a very useful classical interpretation, and students
should read the parts of Slichter’s book [1] which cover this.

The local environment of the nuclei in solids and liquids is influenced by fluctuations, both
static and dynamic, caused by neighboring nuclei and electrons that couple to the nuclear
magnetic moment. These fluctuations will shift and broaden the absorption. Measurement
of these shifts provides information on the static fluctuations in the systems. Measurement
of the width of the line, and the associated relaxation times, provides information on the dy-
namic fluctuations in the system. The most important contribution arises from fluctuations
at the resonance frequency. Thus, NMR provides a method to observe the magnitude of the
local fluctuations at a particular frequency and measurements at several frequencies can be
used to map the fluctuation spectrum.

Water provides an ideal sample for introductory experiments in NMR. The signal from the
hydrogen is quite strong and the properties of the system can be varied over a wide range.
The effect of fluctuations on the NMR signal will be examined in two ways. First, by adding
a magnetic impurity, copper sulfate, to the liquid the strength of the fluctuations can be
changed. Secondly, by solidifying the liquid the characteristic frequency of the temporal
fluctuations can be changed.

The NMR experiment utilizes pulsed techniques to measure the position, width, and relax-
ation time of the resonance. Pulsed techniques, which are now used in most applications,
use linear response theory to relate the response after a short perturbation to the more fa-
miliar continuous absorption method. This experiment also introduces the student to other
important techniques such as high frequency signal transmission, pulse manipulation, and

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signal averaging which is used to recover weak signals from noisy data.

A strong magnetic field will tend to orient nuclear spins and induce a magnetization of
the sample along the direction of the field. The direction of the magnetization can be
changed very efficiently by applying RF pulses at the spin precession frequency, the Larmor
frequency. With an appropriate choice of pulse height, duration and phase the sample can
be brought into any magnetization state desired, but after the pulse it will relax back to
thermal equilibrium, with the magnetization again directed along the field.

One application of NMR is to study the relaxation processes. One distinguishes three types
of relaxation. In the first place there is the interaction with the spins with “the rest of the
system”. The spin distribution is out of thermal equilibrium and will lose energy to the
other degrees of freedom in the system. As a result the magnetization will relax towards
its equilibrium value. The relaxation time associated with these processes is called the
longitudinal relaxation time, τ1 . The second type of relaxation process involves interactions
between the spins. These redistribute energy between the spins but leave the total energy
of the spin system unchanged, so only the components perpendicular to the field relax. The
relevant relaxation time is called transverse relaxation time, τ2 . A third effect is the so
called free induction decay (FID). When the total magnetization by whatever means is put
at some angle with respect to the magnetic field, it starts to precess. If all the spins would
precess at exactly the same frequency, one would observe the transverse component of the
magnetization decay with τ2 . In fact, it seems to decay much faster. Due to variations in its
environment, every spin sees a slightly different field. This means that the local precession
frequencies are slightly different, some spins precess faster than others. However, although it
appears that the transverse magnetization decays, this is not a relaxation process. As long
as there are no interactions, the spins know where they came from, and if all the spins or all
the fields were inverted, the process is perfectly reversible; all the spins precess backward to
where they came from.

The idea of separating the reversible and the irreversible processes is one key feature of pulse
NMR. Typical experiments go as follows. To measure τ2 , rotate, with what is called a π/2
pulse, the magnetization into the x − y plane (z is along the magnetic field). Quickly the
magnetization signal in the x − y plane will disappear. Wait a while, and then, using a pulse
with appropriate amplitude and duration (a π pulse) rotate all the spins by 180◦. Wait a
while longer and the signal reappears; most the spins are back. However, some of the spins
have interacted with other spins, etc. and got lost. Consequently, the echo is smaller than
the original signal, and furthermore, it becomes increasingly smaller when the delay between
the π/2 and the π pulse is increased. From the echo height versus delay time one can obtain
the transverse relaxation time τ2 . A similar experiment is used to measure τ1 . Rotate the
spins by 180◦ so that the magnetization points along the −z axis, wait and rotate them by
90◦ . Now the signal in the x−y plane corresponds to the remaining total magnetization that
you had in the −z direction. Again, with increasing delay this becomes smaller, indicating
how quickly the total magnetization decays. The peak of the FID signal (immediately after
the π/2 pulse) as a function of τ is proportional to | 2 exp (−τ /τ1 ) − 1 | and this may be
used to determine τ1 .

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Before undertaking the actual experiment, it is essential that you find the answers to the
following questions:

1. What is a complex impedance (from AC circuit theory)?

2. What is the characteristic impedance r of a transmission line?

3. What is the impedance Z̃0 at the end (input) of a transmission line if the impedance at
a length l is Z̃l , and the frequency is such that the wavelength in the transmission line is λ?
[Search “transmission line” “input impedance” formula.]

4. What is Z̃0 if Z̃l = r? (Impedance matching)

5. What is Z̃0 if l is a half wavelength (λ/2)?

6. What is Z̃0 if l is a quarter wavelength (λ/4)?

7. For a λ/4 line, what is Z̃0 if Z̃l is open (infinite)?

8. For a λ/4 line, what is Z̃0 if Z̃l is shorted (zero)?

9. What is the behavior of crossed diodes in an NMR circuit?

EQUIPMENT

Electromagnet and HP 6030A Power Supply

SRS DS345 Function Generator

Matec 5100 Gating Modulator (MGM)

Matec 525 RF Gated Amplifier

Matec 625 Broadband Receiver (MBR)

Tektronix TDS2012 Oscilloscope

Pico 3205 PC Oscilloscope and PicoScope6 software

FW Bell 5080 Gaussmeter

Ohaus Explorer Analytical Balance

Coaxial cable

Sample solutions of CuSO4

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PROCEDURE

Caution: Make sure the cooling water is on before using the electromagnet.

NMR samples are placed in a small test tube inside a small coil, which is part of a resonant
circuit, intended to operate around 25MHz.

Connect a coax cable from a function generator to an oscilloscope with a 50 ohm termination.
Observe that the received signal is independent of frequency. Add a cable of length about 2
m with a tee at the oscilloscope, and the other end of the cable open. Observe that the signal
at the oscilloscope is a minimum at a frequency which corresponds to a quarter wavelength
in the 2 m cable. For the NMR experiment, find three coax cables of the same length, about
2 m. Determine the frequency for which these cables are quarter wavelength (around 24.6
MHz). The function generator should be set near this frequency throughout the experiment.
The function generator, with an output amplitude of about 0.5V, should be connected to
the RF Input of the Matec Gating Modulator (MGM). The RF Input Level meter on the
MGM should be just below the red line.

The Gated RF Output of the MGM should be set up as follows: A λ/4 cable should go from
the Gated RF Output to a set of crossed diodes in series, followed by a tee. From one part of
the tee the second λ/4 cable should go to the NMR cell. From the other part of the tee the
third λ/4 cable should lead to the input of the Matec Broadband Receiver (MBR), which
should be shunted to ground with a second set of crossed diodes.

The NMR setup operates in two modes: the transmit mode, when a large amplitude pulse (a
few hundred volts) is present and the crossed diodes act as closed switches, and the receive
mode, when the small NMR signal (less than 0.5V) is present and the crossed diodes act
as open switches. Consider the behavior of the NMR setup with the three λ/4 cables, etc.,
during the transmit mode and the receive mode.

Set the Matec as follows: Sequence Interval, coarse .1-1.1, vernier 1.00 (approximately a
10Hz repetition rate); Pulse Separation, M=100, A=0.00, B=2.0 (∼2 ms separation); Pulse
Width No. 1, coarse .5-10, fine 2.5 (∼2.5 µs width); Pulse Width No. 2, coarse .5-10, fine 6.0
(∼6 µs width); RF Power Low, level 60; Impedance Matching ∼60, RF Tuning 0.0; Pulse
Selector No. 1 switch up, No. 2 switch down, Ext Pulse down; RF Cycle Increment switches
on Continuous; Power switch on, High Voltage switch on.

Place a small probe coil (inside a test tube) into the NMR coil, and monitor it with an
oscilloscope; use a 20 dB, 50 ohm attenuator at the scope, with 1V/div, 1 µs/div settings.
Adjust the MGM Impedance Matching and RF Tuning controls, and the two variable ca-
pacitors in the NMR cell to produce the largest pulse with smooth exponential initiation
and decay. The two variable capacitors are connected in series and parallel with the NMR
coil; the capacitor on the left (looking from the capacitors toward the coil) is in parallel with
the coil, and the capacitor on the right is connected in series between the coil and the coax.
The series capacitor is more important when driving the coil, since it can set the LC series
to resonate at the drive frequency. The parallel capacitor is more important for impedance

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matching the coil circuit with the MBR during the receive mode; the proper way to adjust
the parallel capacitor is to connect the probe coil to the signal generator and adjust the
parallel capacitor for maximum signal out of the MBR.

Place a sample of water with a 0.05 concentration of copper sulfate in the NMR coil. Turn
on the magnet cooling water, and slowly increase the current to 6.30A. Set the Gain of the
Matec Broadband Receiver (MBR) to 9.00, with the Filter at 500 kHz and Multiplier of 0.5.
Trigger the scope with MGM Monitor Pulse No. 1, and monitor the MBR output with the
scope at about 500 mV/div and 500 µs/div. Set the function generator to 25.000 MHz, and
slowly increase the frequency until a maximum, clean exponential free induction decay is
observed on the scope.

Turn Pulse Selector No. 2 switch on, and observe the spin echo. Adjust the pulse widths to
get the best echo. To find T2, use the π/2 - τ - π pulse sequence, and measure the height
of the spin echo as a function of the pulse separation τ . To find τ1 , use a π - τ - π/2 pulse
sequence, and measure the top of the FID following the second pulse as a function of the
pulse separation τ . For all measurements, make sure that the pulse sequence repetition rate
is not too high: increase and/or decrease the MGM sequence interval and see if the pulse
echo changes size (it should not).

Determine τ1 and τ2 as functions of copper sulfate concentration, from about 0.15 down to
0.01 molar concentrations. Throughout your measurements, you should record oscilloscope
images using the PC oscilloscope and software. Other liquid solutions to try include: copper
nitrate (Cu(NO3 )2 ) in water, copper nitrate in methanol, and Zeolite in methanol.

References
[1] C. P. Slichter, Principles of Magnetic Resonance (Harper & Row, New York, 1963).

[2] E. Fukushima and S. B. W. Roeder, Experimental Pulse NMR: A Nuts and Bolts Ap-
proach (Addison-Wesley, Redwood City, 1981).

[3] Thomas C. Farrar, Pulse Nuclear Magnetic Resonance Spectroscopy (Farragut Press,
Chicago, 1989).

[4] D. C. Ailion, Methods of Experimental Physics (Academic Press, New York, Vol. 21,
1983) pp. 439-482.

[5] R. J. Abraham, J. Fisher, and P. Loftus, Introduction to NMR Spectroscopy (John Wiley
& Sons, New York, 1988).