Lecture Note Ii

LECTURE NOTE II
NUCLEAR MAGNETIC RESONANCE
Nuclear magnetic resonance (NMR) is a highly versatile spectroscopic technique with

applications in a large range of disciplines, from chemistry and physics to medicine
including organic chemistry, natural products research, metabolic studies, structural biology,
drug discovery and environmental sciences, owing to its wealth of information about structural,
quantitative and dynamic features. Over the past fifty years nuclear magnetic resonance
spectroscopy, commonly referred to as NMR has become the preeminent technique for
determining the structure of organic compounds. Of all the spectroscopic methods, it is the only
one for which a complete analysis and interpretation of the entire spectrum is normally expected.
Although larger amounts of sample are needed than for mass spectroscopy, NMR is non-
destructive, and with modern instruments good data may be obtained from samples weighing
even less than a milligram.
NMR is a physical phenomenon in which nuclei in a strong constant magnetic field are disturbed
by a weak oscillating magnetic field (in the near field) and respond by producing an
electromagnetic signal with a frequency characteristic of the magnetic field at the nucleus. This
process occurs near resonance, when the oscillation frequency matches the intrinsic frequency of
the nuclei, which depends on the strength of the static magnetic field, the chemical environment,
and the magnetic properties of the isotope involved. In practical applications with static magnetic
fields up to ca. 20 tesla, the frequency is similar to VHF and UHF television broadcasts (60–
1000 MHz). High-resolution nuclear magnetic resonance spectroscopy is widely used to
determine the structure of organic molecules in solution, the study of molecular physics as well
as crystalline and non-crystalline materials. NMR is also routinely used in advanced medical
imaging techniques, such as in magnetic resonance imaging (MRI). The original application of
NMR to condensed matter physics is nowadays mostly devoted to strongly correlated electron
systems.
The nuclei of many elemental isotopes have a characteristic spin (I). Some have integral spins
(e.g., I = 1, 2, 3 ....), some have fractional spins (e.g., I = 1/2, 3/2, 5/2 ....), and a few have no
spin, I = 0 (e.g., 12C, 16O, 32S, ....). Isotopes of particular interest in NMR are 1H, 13C, 19F and 31P,
all of which have I = 1/2. Since the analysis of this spin state is fairly straightforward, our
discussion of NMR will be limited to these and other I = 1/2 nuclei.
The following features lead to the NMR phenomenon:
1. A spinning charge generates a magnetic field, as shown by the animation on the

right.
The resulting spin-magnet has a magnetic moment (μ) proportional to the spin.
2. In the presence of an external magnetic field (B 0), two spin states

exist, +1/2 and -1/2.
The magnetic moment of the lower energy +1/2 state is aligned with the external
field, but that of the higher energy -1/2 spin state is opposed to the external field.
Note that the arrow representing the external field points North.
3. The difference in energy between the two spin states is dependent on the external magnetic field strength, and is
always very small. The following diagram illustrates that the two spin states have the same energy when the external
field is zero, but diverge as the field increases. At a field equal to B x a formula for the energy difference is given
(remember I = 1/2 and μ is the magnetic moment of the nucleus in the field).
Because strong magnetic fields are necessary for NMR spectroscopy and the earth's magnetic field is not constant
(approximately 10-4 T) at ground level, modern NMR spectrometers use powerful magnets having fields of 1 to 20
T. Even with these high fields, the energy difference between the two spin states is less than 0.1 cal/mole. This small
energy difference (ΔE) is usually given as a frequency in units of MHz (10 6 Hz), ranging from 20 to 900 MHz
depending on the magnetic field strength and the specific nucleus being studied. Irradiation of a sample with radio
frequency (rf) energy corresponding exactly to the spin state separation of a specific set of nuclei will cause
excitation of those nuclei in the +1/2 state to the higher -1/2 spin state.
Note: This electromagnetic radiation falls in the radio and television broadcast spectrum. NMR spectroscopy
is therefore the energetically mildest probe used to examine the structure of molecules.
The nucleus of a hydrogen atom (the proton) has a magnetic moment μ = 2.7927, and has been studied more
than any other nucleus. The previous diagram may be changed to display energy differences for the proton
spin states (as frequencies) by mouse clicking anywhere within it.
4. For spin 1/2 nuclei the energy difference between the two spin states at a given magnetic field strength will be
proportional to their magnetic moments. For the four common nuclei noted above, the magnetic moments are: 1H μ
= 2.7927, 19F μ = 2.6273, 31P μ = 1.1305 & 13C μ = 0.7022. These moments are in nuclear magnetons, which are
5.05078•10-27 JT-1. The following diagram gives the approximate frequencies that correspond to the spin state energy
separations for each of these nuclei in an external magnetic field of 2.35 T. The formula in the colored box shows
the direct correlation of frequency (energy difference) with magnetic moment (h = Planck's constant = 6.626069•10 -
34
Js).
The principle of NMR usually involves three sequential steps:
 The alignment (polarization) of the magnetic nuclear spins in an applied, constant

magnetic field B0.
 The perturbation of this alignment of the nuclear spins by a weak oscillating
magnetic field, usually referred to as a radio frequency (RF) pulse. The oscillation
frequency required for significant perturbation is dependent upon the static magnetic
field (B0) and the nuclei of observation. The two magnetic fields are usually chosen
to be perpendicular to each other as this maximizes the NMR signal strength.
 The detection of the NMR signal during or after the RF pulse, is due to the voltage
induced in a detection coil by precession of the nuclear spins around B0. After an RF
pulse, precession usually occurs with the nuclei's Larmor frequency and, in itself,
does not involve transitions between spin states or energy levels.
PROTON NMR SPECTROSCOPY

This important and well-established application of nuclear magnetic resonance will serve to
illustrate some of the novel aspects of this method. To begin with, the NMR spectrometer must
be tuned to a specific nucleus, in this case, the proton. The actual procedure for obtaining the
spectrum varies, but the simplest is referred to as the continuous wave (CW) method. A typical
CW-spectrometer is shown in the following diagram. A solution of the sample in a uniform 5
mm glass tube is oriented between the poles of a powerful magnet, and is spun to any average
magnetic field variations, as well as tube imperfections. Radio frequency radiation of appropriate
energy is broadcast into the sample from an antenna coil (colored red). A receiver coil surrounds
the sample tube, and emission of absorbed rf energy is monitored by dedicated electronic devices
and a computer. An NMR spectrum is acquired by varying or sweeping the magnetic field over a
small range while observing the rf signal from the sample. An equally effective technique is to
vary the frequency of the rf radiation while holding the external field constant.
Figure showing a typical set up of the proton NMR spectroscopy

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LECTURE NOTE II

NUCLEAR MAGNETIC RESONANCE

Nuclear magnetic resonance (NMR) is a highly versatile spectroscopic technique with

The following features lead to the NMR phenomenon:

1. A spinning charge generates a magnetic field, as shown by the animation on the

2. In the presence of an external magnetic field (B 0), two spin states

 The alignment (polarization) of the magnetic nuclear spins in an applied, constant

PROTON NMR SPECTROSCOPY

Figure showing a typical set up of the proton NMR spectroscopy

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