Nuclear Magnetic Resonance Spectroscopy

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Books:

❑ Introduction to Spectroscopy by Donald Pavia, Gary Lampman, George Kriz and

James Vyvyan

❑ Solving Problems with NMR Spectroscopy: Atta-Ur-Rahman, Muhammad Iqbal

Choudhary and Atia-Tul-Wahab

❑ Fundamentals of Molecular Spectroscopy by Colin N. Banwell and Elaine M. Mccash

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 What is NMR Spectroscopy?

➢ Nuclear Magnetic Resonance Spectroscopy

➢ Something to do with the magnetic properties of the nuclei

➢ We will see later what is meant by resonance

Each atomic nucleus has four important

physical properties:
1. Mass
2.Electric charge
3. Magnetism
4. Spin

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❑ Nuclear magnetism and nuclear spin, are much less evident

❑ The bulk magnetism of some materials, such as iron, is due to the electrons, not to the
nuclei

➢ Magnetic properties of materials are dominated by electrons

➢ Essentially the electrons are much more magnetic than nuclei

➢ It is rather surprising that much weaker magnetic properties of nuclei in the

presence of more magnetic electrons are used in NMR for finding the structure
of molecules

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 ➢ NMR spectroscopy is related to nuclear magnetism

➢ Nuclear magnetism arises from the magnetic properties of protons and neutrons

➢ The magnetic properties of proton and neutron are due to spin angular momentum (I)

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➢ NMR spectroscopy is the study of interaction of radiofrequency (Rf) electromagnetic
radiation with the nuclei of molecules placed in a strong magnetic field

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➢ Zeeman first observed the strange behaviour of certain
nuclei when subjected to strong magnetic field at the end of
19th Century-Zeeman Effect

➢ NMR spectrometers were commercially available only in

1950s
Pieter Zeeman
Netherlands
Nobel Prize (1902, Physics)

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 Historical Perspective: The Birth of NMR

❑ In December 1945, Edward Mills Purcell at Harvard

University detected the first solid-state NMR signal in 1 kg of
paraffin wax

❑ Almost simultaneously Felix Bloch at Stanford University

carried out the first liquid-state NMR experiment in water. E. M. Purcell

❑ Purcell and Bloch shared the Nobel Prize in Physics in 1952.

❑ It is a remarkable fact that the discovery, development and
applications of NMR have resulted in no less than 8 Nobel
laureates in Physics, Chemistry and Medicine!
F. Bloch

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For an electron……

➢ Conventional angular momentum: Arises from its motion; orbital angular momentum
due to its circulating motion around the nucleus

➢ Intrinsic or spin angular momentum which arises from nothing, being simply a
feature of the electron's nature and which is always same for an electron namely ½
➢ There is no such concept as the rotation of electron around its own axis, its only
spin
➢ Spin is an abstract quantum-mechanical description

➢ In a similar way certain nuclei have spin angular momentum (spin)

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➢ The magnetic properties of proton and neutron are due to spin angular momentum (I)

Proton Neutron

I 1/2 1/2

➢ Effective magnetic moment of a nucleus is a resultant of proton and neutron spins

➢ NMR deals with nuclei having I ≠ 0

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 Macroscopic Magnetism

The magnetic energy of a small object depends on the interaction between its magnetic
moment with the external magnetic field

A bar magnet just orients itself

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 Nuclear Spins in a Magnetic Field

➢ Quantum mechanics impose some restrictions on the possible orientations of the spin
➢ When placed in an magnetic field, they will adopt one of the (2I+1) quantized
orientations
➢ The projections along z direction can only have integer or half-integer values

Larmor Precession

➢It starts precessing around the magnetic field

➢ But it can precess only with certain angles with respect to the applied magnetic field
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 Interaction of Nuclear Spins with Magnetic Field

➢ Nuclear magnetic moment arises from spin angular momentum

γ: gyromagnetic ratio
I: spin angular quantum number

➢ The magnetic field B0 is applied along z axis

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 Interaction Energy: Magnetic Field and Nuclear Magnetic Moment

Nuclear Zeeman Splitting

➢ Splitting of a spectral line in the presence of a static magnetic field into several
components

Pieter Zeeman
Netherlands
Aurora Borealis
Nobel Prize (1902, Physics)
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 Nuclear Zeeman Splitting

➢ A nuclear state with spin I is (2I+1) fold degenerate

➢ Magnetic field breaks this degeneracy

➢ NMR is the spectroscopy of Nuclear Zeeman Sublevels

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 Interaction Energy: Magnetic Field and Nuclear Magnetic Moment

Let’s consider a 1H nucleus (I = 1/2 )

What is the energy difference between the spin states in a spin 1/2 system?

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