LECTURE NOTE PREPARED BY DR.

SUPRIYO SAHA

Nuclear Magnetic Resonance Spectroscopy

 Nuclear Magnetic Resonance (NMR) spectroscopy is a process whereby energy from an
external source is absorbed and brings about a change or resonance to an ‘excited’ or
high energy state.
 The energy required for NMR lies in the low energy or long wavelength radio-frequency
end of the electromagnetic spectrum.
 The magnetic properties of nuclei arising from the axial spin, the emerging
radiofrequency
gets absorbed in a magnetic field.
 NMR absorption spectrum invariably comprises one to several groups of absorption lines
in the ratio-frequency portion of the electromagnetic spectrum.
 The location of peaks indicate the chemical nature of the nucleus, whereas the multiplets
provide information regarding the spatial positions of the neighboring nuclei.
 NMR has accomplished a growth in a geometrical progression since the early sixties and
virtually developed into extremely potential analytical tools not only useful for
elucidation of complex structural determinations.

Phenomenon behind Nuclear Magnetic Resonance Spectroscopy

Five different aspects that essentially govern the NMR phenomenon:
i. The Spinning Nucleus:

 The nucleus of the hydrogen atom, i.e., the proton, just behaves as if it is a small spinning
bar magnet.
 It does so because it evidently possesses an electrical charge as well as a mechanical spin.
 Consequently, a spinning charged body will generate a magnetic field, and hence the
nucleus of hydrogen atom is not an exception.

ii. The effect of an External Magnetic Field:

 The proton not only responds to the influence of an external magnetic field but also tends
to align itself with that field.
  However, because of restrictions as applicable to nuclei the proton can only adopt the
following two orientations with external magnetic field.

At this point two situations normally arise, namely:

a. When proton is aligned with the field (i.e., at lower energy state).

b. When proton is opposed to the field (i.e., at higher energy state).

iii. The Precessional Motion:

The proton appears to be behaving as ‘spinning magnet’ and therefore, not only can it align
itself with or oppose an external field, but also may move in a characteristic manner under the
influence of the external magnet.

The above figure represents:

 Application of external magnetic field to the nucleus.

 After the absorption of energy, proton from low energy level is proceed to high energy
level.
 The spinning of protons are opposite to each other.
However, the energy of the reorientation of magnetic dipole, ΔE is expressed by Planck’s
equation

ΔE = hν. where, h = Planck’s constant, and ν = Frequency of radiation.

 The top movement will perform a comparatively slower with the spinning axis of the top
moves slowly around the vertical.
 This particular phenomenon is known as the precessional motion and hence, the ‘top’ is
generally said to be precessing around the vertical axis of the earth’s gravitational field.
 In other words, the precession comes into effect due to the interaction of spin (i.e.,
gyroscopic motion) with the earth’s gravity vertically downwards.
 Therefore, a spinning top will precess, whereas a static top will fall over (not precess).

iv. The Precessional Frequency:

 The spinning frequency of the nucleus does not change at all whereas the speed of
precession does change.
 Therefore, ν ∝ Bo (external magnetic field), i.e., the precessional frequency is directly
proportional to the strength of the external field Bo.

v. The Energy Transitions:

 Whenever a proton is precessing in the aligned orientation (low energy) it can absorb
energy and pass into the orientation (high energy).
 Subsequently it can lose this extra energy and relax back into the aligned state.
 Interestingly, the precessing proton can only absorb energy from the radio frequency
source if the precessing frequency is exactly the same as that of the radio frequency
beam.
 When this particular situation arises, the nucleus and the radio frequency beam are said to
be in resonance, thereby justifying the term ‘nuclear magnetic resonance’.
 In NMR spectroscopy, the precessing protons of an organic molecule, after being duly
exposed to a powerful external magnetic field (ranging between 60-400 MHz), are
irradiated with radio frequency energy of the appropriate frequencies, thereby promoting
protons from the low-energy (aligned state) to the high energy (opposed state).