Nuclear Magnetic Resonance

There is always a small excess of nuclei (surplus population) aligned with the field
(ground state) than pointing against it (excited state) according to the Boltzmann
distribution law. The surplus population (excess number of spins, also known as
population difference [number of molecules at the ground state – number of molecules
in the excited state], N  Nβ), is considerably small when compared to the population
molecular spectroscopy methods, UV-Vis spectroscopy or IR spectroscopy.

Crudely, we can think of the nuclei as being spinning around its z axis. What is
precession, 0, associated with? Now, if we bring about the applied laboratory magnetic
field, B0, there will be an interaction between µ and B0 that generates a torque (angular
force). No matter which is the original direction of µ, it will tend to align () with B0 or
against (β) it. Since the nuclei associated with µ are spinning due to the spin angular
momentum, l, there are two forces (torque and gravity) acting on it. One that wants to
bring it towards B0 , and one that wants to keep it spinning. µ ends up precessing
around B0: i.e., µ  B0 . The best way to picture it is to imagine a similarity, a spinning
wooden top under the action of gravity. The frequency at which µ precesses around B o
is the same.

We see the effects on macroscopic magnetization, M0, which is directly proportional to

the surplus number of nuclear spins at the ground state, viz., the population difference
(N  Nβ), in which contributions from different µs have been averaged. We can
decompose each magnetic moment, µ as their components a z component and an <xy>
plane components (x & y components combined). The components in the <xy> plane are
randomly distributed (positive and negative directions‟ components) and cancel out. For
the component along the z-direction, we get a net magnetization, M0 proportional to (N
 Nβ). we will from now on use M0 in all further description. There is an important
difference between a µ and M0. While the former (µ) is quantized and can be only in one
of two states ( or β), the latter (M0) tells us on the whole spin population. It has a
continuous number of states. We need the system to absorb energy. The energy source is
an oscillating electromagnetic radiation (B1), the radiofrequency pulse.

Let us imagine a scenario: We are standing on the pavement adjacent to a road,

waiting for a specific bus. We are also viewing another slow-moving bus with lot of
passengers, is passing (left to right) on the road. For the people standing on the
pavement (laboratory frame of reference), all those people sitting in the bus will appear
as moving in the direction (left to right). Now, if we think that we are sitting in the bus
(rotating frame of reference), then for the people sitting in the bus, the fellow
passengers sitting over the other seats in the same bus will all appear stationary, since
all of us are moving at the same velocity in the same direction.

Whereas, for the people sitting in the bus (rotating frame of reference), the people on
the pavement (laboratory frame of reference) are moving at the same velocity but in the
opposite direction. That‟s why rather viewing the moving things from the stationary
position, if we imagine we are also precessing (rotating frame of reference) at the
frequency of the precessing nuclei, then for us all precessing nuclei will appear like
stationary. That‟s why, while studying pulsed NMR, it is easy to understand things
(interactions of spins), when we imagine the rotating frame of reference. Further with
the application of additional force in the form an NMR pulse, when the collective
behavior of spins (surplus spins at the ground state) as magnetization becomes easy to
follow. Because with the application of an NMR pulse, now our Magnetization
experiences the laboratory „constant‟ magnetic field, B0, and an additional oscillating
magnetic field, B1, of the „bunched‟ electromagnetic radiation, as radiofrequency pulse.
Therefore, due to the application of a radiofrequency pulse, the magnetization exhibits
nutation (a periodic variation in the uniform precession of the axis of a spinning
[precessing] system), i.e., moving perpendicularly to the additional deflecting force. BY
moving into the rotating frame of reference, during an NMR experiment, we can for the
time being ignore the effects of laboratory magnetic field and focus on only one force,
i.e., the effects of osciallating magnetic field, B1, when it is applied.

Inversion recovery experiment emphasizes the measurement of T1 relaxation time. In

an inversion recovery experiment, an initial 180-degree RF pulse inverts the Mz
longitudinal magnetization to –Mz . After a delay time known as the time of inversion, a
90-degree RF pulse rotates the recovered fraction of Mz spins into the transverse plane
to generate the FID. A time delay (time of inversion) between excitation pulses allows
recovery of the longitudinal magnetization by allowing the nuclear spin system in the
excited state to interact with the surrounding (lattice) to transmit the „excess‟ energy in
a non-radiative manner. By incrementally increasing the time delay, for each
experiment (we need to perform 1024 experiments), we can allow the system to interact
with the surrounding sufficiently for longer duration so that the magnetization slowly
grows back to the original magnetization along the +z-direction (Mz). T1 is the
“longitudinal” relaxation time constant which results from “spin-lattice” relaxation.

Spin echo describes the excitation of protons‟ magnetization in a sample with an RF

(radio-frequency) pulse (90) and production of the FID (free induction decay), followed
by a time delay and subsequently a second RF pulse (180) to produce an echo.
Incremental increase in the timing between the RF pulses allows the nuclear spin
system to interact with other similar spins to exchange energy in an non-radiative
manner so that the system „relaxes‟ back to the equilibrium, i.e., along the <xy> plane,
the magnetization, Mxy ultimately becomes zero. Normally, we can perform 1024 spin echo
experiments where the time of repetition (TR), which typically ranges from about 24 to 3,600
msec (in every experiment, there will be an incremental increase in the time delay between /2
and  pulse). Spin echo experiment allows us to measure the spin-spin relaxation time constant
(T2). Line widths are related to T2 relaxation. Line Width ~ 1/ T2 . T2 is always faster
(shorter) than (in liquids) or equal to T1 (viscous systems or occasionally in solid-state
systems such as zeolites).