NUCLEAR MAGNETIC RESONANCE

INTRODUCTIN

In 1946, NMR was co-discovered by Purcell, Pound and Torrey of Harvard University and Bloch, Hansen
and Packard of Stanford University. The discovery first came about when it was noticed that magnetic
nuclei, such as 1H and 31P (read: proton and Phosphorus 31) were able to absorb radio frequency
energy when placed in a magnetic field of a strength that was specific to the nucleus. Upon absorption,
the nuclei begin to resonate and different atoms within a molecule resonated at different frequencies.
This observation allowed a detailed analysis of the structure of a molecule. Since then, NMR has been
applied to solids, liquids and gasses, kinetic and structural studies, resulting in 6 Nobel prizes being
awarded in the field of NMR

Nuclear magnetic resonance (NMR) is a physical phenomenon in which nuclei in a

strong constant magnetic field are perturbed 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.

 Nuclear magnetic resonance spectroscopy is widely used to determine the structure of organic
molecules in solution and study molecular physics and crystals as well as non-crystalline materials.
NMR is also routinely used in advanced medical imaging techniques, such as in magnetic resonance
imaging (MRI).

FOR WHICH MATERIAL WE CAN TAKE NMR

 In order to interact with the magnetic field in the spectrometer, the nucleus must have an
intrinsic nuclear magnetic moment and angular momentum. This occurs when an isotope has a
nonzero nuclear spin, meaning an odd number
of protons and/or neutrons (see Isotope). Nuclides with even numbers of both have a total spin of
zero and are therefore NMR-inactive.

PRINCIPLE

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 detection of the NMR signal during or after the RF pulse, 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 intrinsic Larmor frequency and, in itself, does not
involve transitions between spin states or energy levels

Theory of NMR
 All nucleons, that is neutrons and protons, composing any atomic nucleus, have the intrinsic
quantum property of spin, an intrinsic angular momentum analogous to the classical angular
momentum of a spinning sphere. The overall spin of the nucleus is determined by the spin
quantum number S. If the numbers of both the protons and neutrons in a given nuclide are
even then S = 0, i.e. there is no overall spin. Then, just as electrons pair up in
nondegenerate atomic orbitals, so do even numbers of protons or even numbers of neutrons
(both of which are also spin-1/2 particles and hence fermions), giving zero overall spin.[citation
needed]

 However, a proton and neutron spin vector that aligns itself opposite to the external magnetic
field vector will have a lower energy when their spins are parallel, not anti-parallel. This
parallel spin alignment of distinguishable particles does not violate the Pauli exclusion
principle. The lowering of energy for parallel spins has to do with the quark structure of these
two nucleons.[citation needed] As a result, the spin ground state for the deuteron (the nucleus
of deuterium, the 2H isotope of hydrogen), which has only a proton and a neutron,
corresponds to a spin value of 1, not of zero. On the other hand, because of the Pauli
exclusion principle, the tritium isotope of hydrogen must have a pair of anti-parallel spin
neutrons (of total spin zero for the neutron-spin pair), plus a proton of spin 1/2 . Therefore, the
tritium total nuclear spin value is again 1/2 , just like for the simpler, abundant hydrogen
isotope, 1H nucleus (the proton). The NMR absorption frequency for tritium is also similar to
that of 1H. In many other cases of non-radioactive nuclei, the overall spin is also non-zero.
For example, the 27
Al
 nucleus has an overall spin value S = 5⁄2.
A non-zero spin  is always associated with a non-zero magnetic dipole moment, , via the relation

where γ is the gyromagnetic ratio. Classically, this corresponds to the proportionality between

the angular momentum and the magnetic dipole moment of a spinning charged sphere, both of
which are vectors parallel to the rotation axis whose length increases proportional to the spinning
frequency. It is the magnetic moment and its interaction with magnetic fields that allows the
observation of NMR signal associated with transitions between nuclear spin levels during
resonant RF irradiation or caused by Larmor precession of the average magnetic moment after
resonant irradiation. Nuclides with even numbers of both protons and neutrons have
zero nuclear magnetic dipole moment and hence do not exhibit NMR signal. For instance, 18
O
 is an example of a nuclide that produces no NMR signal, whereas  and 37Cl
 are nuclides that do exhibit NMR spectra. The last two nuclei have spin S > 1/2 ‘

Nuclear Energy Levels

As mentioned above, an exact quanta of energy must be used to induce the spin flip or
transition. For any m, there are 2m+1 energy levels. For a spin 1/2 nucleus, there are only two
energy levels, the low energy level occupied by the spins which aligned with B0B0 and the high
energy level occupied by spins aligned against B0B0. Each energy level is given by

E=−mℏγB0(2)(2)E=−mℏγB0
where mm is the magnetic quantum number, in this case +/- 1/2. The energy levels
for m>1/2m>1/2, known as quadrupolar nuclei, are more complex and information regarding
them can be found here.

The energy difference between the energy levels is then

ΔE=ℏγB0(3)(3)ΔE=ℏγB0

where ℏℏ is Planks constant.

A schematic showing how the energy levels are arranged for a spin=1/2 nucleus is shown
below. Note how the strength of the magnetic field plays a large role in the energy level
difference. In the absence of an applied field the nuclear energy levels are degenerate. The
splitting of the degenerate energy level due to the presence of a magnetic field in known
as Zeeman Splitting.

Figure :
The splitting of the degenerate nuclear energy levels under an applied magnetic field. The green
spheres represent atomic nuclei which are either aligned with (low energy) or against (high energy)
the magnetic field.

Energy Transitions (Spin Flip)

In order for the NMR experiment to work, a spin flip between the energy levels must occur. The
energy difference between the two states corresponds to the energy of the electromagnetic
radiation that causes the nuclei to change their energy levels. For most NMR
spectrometers, B0B0 is on the order of Tesla (T) while γγ is on the order of 107107.
Consequently, the electromagnetic radiation required is on the order of 100's of MHz and even
GHz. The energy of a photon is represented by

E=hν(4)(4)E=hν
and thus the frequency necessary for absorption to occur is represented as:

ν=γB02π(5)(5)ν=γB02π

For the beginner, the NMR experiment measures the resonant frequency that causes a spin flip.
For the more advanced NMR users, the sections on NMR detection and Larmor
frequency should be consulted.

Figure : Ab
sorption of radio frequency radiation to promote a transition between nuclear energy levels, called
a spin flip.

Nuclear Shielding

The power of NMR is based on the concept of nuclear shielding, which allows for structural
assignments. Every atom is surrounded by electrons, which orbit the nucleus. Charged particles
moving in a loop will create a magnetic field which is felt by the nucleus. Therefore the local
electronic environment surrounding the nucleus will slightly change the magnetic field
experienced by the nucleus, which in turn will cause slight changes in the energy levels! This is
known as shielding. Nuclei that experience different magnetic fields due to the local electronic
interactions are known as inequivalent nuclei. The change in the energy levels requires a
different frequency to excite the spin flip, which as will be seen below, creates a new peak in
the NMR spectrum. The shielding allows for structural determination of molecules.
 Figure 44:
The effect that shielding from electrons has on the splitting of the nuclear energy levels. Electrons impart
their own magnetic field which shields the nucleus from the externally applied magnetic field. This effect
is greatly exaggerated in this illustration.

The shielding of the nucleus allows for chemically inequivalent environments to be determined
by Fourier Transforming the NMR signal. The result is a spectrum, shown below, that consists
of a set of peaks in which each peak corresponds to a distinct chemical environment.
The area underneath the peak is directly proportional to the number of nuclei in that chemical
environment. Additional details about the structure manifest themselves in the form of
different NMR interactions, each altering the NMR spectrum in a distinct manner. The x-axis of
an NMR spectrum is given in parts per million (ppm) and the relation to shielding is
explained here.
 Fig
ure :  P spectrum of phosphinic acid. Each peak corresponds to a distinct chemical
31

environment while the area under the peak is proportional to the number of nuclei in a
given environment.