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Nuclear Magnetic Resonance (NMR)

Spectroscopy
Introduction

Nuclei with an odd number of protons, neutrons, or both, will have an instrinsic nuclear
spin.
Spin quantum number for various nuclei
Number of protons Number of Neutrons Spin Quantum Number Examples
12
Even Even 0 C, 16O, 32S
1
Odd Even 1/2 H, 19F, 31P
11
" " 3/2 B,35Cl, 79Br
13
Even Odd 1/2 C
127
" " 3/2 I
17
" " 5/2 O
2
Odd Odd 1 H, 14N

When a nucleus with a non-zero spin is placed in a magnetic field, the nuclear spin can
align in either the same direction or in the opposite direction as the field. These two
nuclear spin alignments have different energies and application of a magnetic field lifts
the degeneracy of the nuclear spins. A nucleus that has its spin aligned with the field will
have a lower energy than when it has its spin aligned in the opposite direction to the field.
Nuclear magnetic resonance (NMR) spectroscopy is the absorption of radiofrequency
radiation by a nucleus in a strong magnetic field. Absorption of the radiation causes the
nuclear spin to realign or flip in the higher-energy direction. After absorbing energy the
nuclei will reemit RF radiation and return to the lower-energy state.

The energy of a NMR transition depends on the magnetic-field strength and a


proportionality factor for each nucleus called the magnetogyric ratio. The local
environment around a given nucleus in a molecule will slightly perturb the local magnetic
field exerted on that nucleus and affect its exact transition energy. This dependence of the
transition energy on the position of a particular atom in a molecule makes NMR
spectroscopy extremely useful for determining the structure of molecules.

Instrumentation

There are two NMR spectrometer designs, continuous-wave (cw), and pulsed or Fourier-
transform (FT-NMR). CW-NMR spectrometers have largely been replaced with pulsed
FT-NMR instruments. However due to the lower maintenance and operating cost of cw
instruments, they are still commonly used for routine 1H NMR spectroscopy at 60 MHz.
(Low-resolution cw instruments require only water-cooled electromagnets instead of the
liquid-He-cooled superconducting magnets found in higher-field FT-NMR
spectrometers.) These two spectrometer designs are described in separate CW-NMR and
FT-NMR documents.

Continuous-Wave Nuclear Magnetic


Resonance (NMR) Spectroscopy
Introduction

Continuous-wave NMR spectrometers have largely been replaced with pulsed FT-NMR
instruments. However due to the lower maintenance and operating cost of cw
instruments, they are still commonly used for routine 1H NMR spectroscopy at 60 MHz.
(Low-resolution cw instruments require only water-cooled electromagnets instead of the
liquid-He-cooled superconducting magnets found in higher-field FT-NMR
spectrometers.)

Instrumentation

A cw-NMR spectrometer consists of a control console, magnet, and two orthogonal coils
of wire that serve as antennas for radiofrequency (RF) radiation. One coil is attached to
an RF generator and serves as a transmitter. The other coil is the RF pick-up coil and is
attached to the detection electronics.

Since the two coils are orthogonal, the pick-up coil cannot directly recieve any radiation
from the generator coil. When a nucleus absorbs RF radiation, it can become reoriented
due to its normal movement in solution and re-emit the RF radiation is a direction that
can be recieved by the pick-up coil. This orthogonal coil arrangement greatly increases
the sensitivity of NMR spectroscopy, similar to optical fluorescence.

Spectra are obtained by scanning the magnet and recording the pick-up coil signal on
paper at the control console.

Fourier-Transform Nuclear Magnetic


Resonance (FT-NMR) Spectroscopy
Introduction

Fourier-transform NMR spectrometers use a pulse of radiofrequency (RF) radiation to


cause nuclei in a magnetic field to flip into the higher-energy alignment. Due to the
Heisenberg uncertainty principle, the frequency width of the RF pulse (typically 1-10 µs)
is wide enough to simultaneously excite nuclei in all local environments. All of the nuclei
will re-emit RF radiation at their respective resonance frequencies, creating an
interference pattern in the resulting RF emission versus time, known as a free-induction
decay (FID). The frequencies are extracted from the FID by a Fourier transform of the
time-based data.

Instrumentation
An FT-NMR spectrometer consists of a control console, magnet, and a coil of wire that
serves as the antenna for transmitting and receiving the RF radiation. (Only one coil is
necessary because signal reception does not begin until after the end of the excitation
pulse.) Because the FID results from the emission due to nuclei in all environments, each
pulse contains an interference pattern from which the complete spectrum can be obtained.
Because of this multiplex (or Fellgett) advantage, repetitive signals can be summed and
averaged to greatly improve the signal-to-noise ratio of the resulting FID.