• Nuclei with an odd mass or odd atomic number have "nuclear spin" (in a similar

fashion to the spin of electrons). This includes 1H and 13C (but not 12C).

•   The NMR behaviour of 1H and 13C nuclei has been exploited by organic chemist
since they provide valuable information that can be used to deduce the structure of
organic compounds.

• Since a nucleus is a charged particle in motion, it will develop a magnetic field.  1H

and 13C  have nuclear spins of 1/2 and so they behave in a similar fashion to a simple,
tiny bar magnet. 

• In the absence of a magnetic field, these are randomly oriented but when a field is
applied they line up parallel to the applied field, either spin aligned or spin opposed. 

• The more highly populated state is the lower energy spin state spin aligned situation. 

• In NMR, electromagnetic (EM) radiation is used to "flip" the alignment of nuclear

spins from the low energy, spin aligned state to the higher energy spin opposed state. 
• The energy required for this transition depends on the strength of the applied
magnetic field.

• The energy difference between the spin states is quite small and corresponds to the
radio frequency range of the EM spectrum.

• The energy required to cause the spin-flip, ΔE, depends on the magnetic field strength
at the nucleus.

• With no applied field, there is no energy difference between the spin states, but as the
field increases, so does the separation of energies of the spin states and therefore the
frequency required to cause the spin-flip also increases.

• ΔE’> ΔE since Ho’> Ho

The basic arrangement of an NMR spectrometer

• The sample is positioned in the magnetic field and excited via pulsations in the radio
frequency input circuit. The realigned magnetic fields induce a radio signal in the
 output circuit which is used to generate the output signal. Fourier analysis of the
complex output produces the actual spectrum. The pulse is repeated as many times as
necessary to allow the signals to be identified from the background noise

Chemical Shift

• An NMR spectrum is a plot of the radio frequency applied against absorption.

• A signal in the spectrum is referred to as a resonance. The frequency of a signal is

known as its chemical shift, δ.

• The chemical shift of a nucleus is the difference between the resonance frequency of
the nucleus and a standard, relative to the standard. This quantity is reported in ppm
and given the symbol δ.

•
• Typically for field strength of 4.7 T the resonance frequency of a proton will occur
around 200 MHz and for a carbon, around 50.4 MHz. The reference compound is the
same for both, Tetramethysilane (Si(CH3)4).

Population of energy (nuclear spin ) levels

• The energy difference ΔE(gNβNBo) between the two spin states is very small and
hence nuclei may occupy either states almost equally. However, there will always be
a slight excess of nuclei in the lower energy level governed by Boltzmann distribution
law and temperature. The population of these levels can be given by the expression;

• Nβ/Nα= e -ΔE/kT

• where Nβ is the No. of nuclei in the β- spin state and Nα is the No. of nuclei in the α-
spin state

• ΔE= gNβNBo

• Nβ/Nα= e -ΔE/kT = e - gNβNBo /kT

• Thus at all temperatures above absolute zero, the upper level will always be populated
to some extent, although for large ΔE population may be insignificant.
• In general, a charged particle spinning about an axis constitutes a circular electric
current, which in turn produces a magnetic dipole. In other words, the spinning
particle behaves as a tiny bar magnet placed along the spin axis(Fig. 1)

• The size of the dipole (i.e. strength of the magnet) is proportional to the spin angular
momentum where

• γ is a fundamental constant, called the magnetogyric ratio, and has characteristic

values for each nucleus.

• In general there are four different features of a NMR spectrum which provide
important information about the structure of a compound.

• Number of signals : The number of signals gives the information about how many
different types of hydrogens are present.

• Position of signals (Chemical shift) :The value of chemical shift is determined by

the nearby environment of each hydrogen and thus we get information about the local
electronic surroundings for each hydrogen.

• Intensity of signals: The intensities of the signals tell us the number of identical
hydrogens.

• Spin-spin splitting of signals: The splitting of each signal tells about the other
groups present in the proximity to that particular hydrogen.
• An NMR spectrum is a plot of the intensity of a peak against chemical shift, measured
in parts per million (ppm).

• Chemical shifts are reported on the horizontal axis of the spectrum. Most protons
absorb between 0-12 ppm. The terms “upfield” and “downfield” describe the relative
location of peaks. Upfield means the low value of chemical shift (right side) and
downfield means the high value of chemical shift (left side)

• In a molecule each type of proton has a different electronic environment and shows
signal at different value of chemical shift. All these values are measured relative to
the position of a reference peak at 0 ppm on the δ scale due to Tetramethylsilane
(TMS). TMS is a volatile inert compound that gives a single peak at 0 ppm.

Magnet

• The heart of the NMR spectrometer is the magnet.

• Modern high-field NMR spectrometers have oscillators with frequencies of up to 750

MHz, and intensive efforts are under way to develop magnets with higher oscillator
frequencies.

• The solenoid in these magnets is made of a niobium alloy wire dipped in liquid
helium (-269oC) At this temperature the resistance to electron flow is zero, so, once
charged, the "superconducting" magnets become permanently magnetized without
consuming any electricity.

• The liquid helium is housed in an inner container, with liquid nitrogen in an outer
container to minimize the loss of helium by evaporation.

• A large balloon can be connected to the magnet to collect the evaporated helium gas,
for subsequent liquefaction and recycling.

• In places where liquid helium is not readily available, it is advisable to order special
larger magnet Dewars with the instrument, with longer helium hold times.

• Fitted with such special Dewars, 300-MHz instruments need to be refilled only about
once a year; on 500-MHz instruments the refill period is about once in 4-5 months.
• Superconducting magnets are very stable, allowing measurements to be made over
long periods with little or no variation of the magnetic field.

PROBE

• The probe, situated between the field gradient coils in the bore of the magnet, consists
of a cylindrical metal tube that transmits the pulses to the sample and receives the
resulting NMR signals.

• The glass tube containing the sample solution is lowered gently onto a cushion of air
from the top of the magnet into the upper regions of the probe.

• The probe, which is inserted into the magnet from the bottom of the cryostat, is
normally kept at room temperature, as is the sample tube.

• The sample is spun on its axis in a stream of air to minimize the effects of any
magnetic field in homogeneities.

• The glass tube containing the sample solution is lowered gently onto a cushion of air
from the top of the magnet into the upper regions of the probe.

• The probe, which is inserted into the magnet from the bottom of the cryostat, is
normally kept at room temperature, as is the sample tube.

• The sample is spun on its axis in a stream of air to minimize the effects of any
magnetic field in homogeneities.

• The gradient coils are also kept at room temperature. If only 1H-NMR spectra are to
be recorded, then it is advisable to use a dedicated 1H probe that affords maximum
sensitivity.

• If, however, 13C-NMR spectra are also to be recorded frequently, as is usually the
case, then a dual 1H/13C probe is recommended, which, although having a somewhat
(10-20%) lower sensitivity than the dedicated probe, has the advantage of avoiding
frequent changing of the probe, retuning, and reshimming.

• If other nuclei (e.g., 19F, 31P) are to be studied, then broadband multinuclear probes can
be used, although the sensitivity of such probes is lower by a factor of about 2 than
that of dedicated probes.
• Spin –spin splitting or spin-spin coupling or multiplicity of signals

• The splitting of an NMR signal in to a number of sub-peaks is due to the

different environment of the absorbing protons with respect to nearby protons
(i.e., protons attached to adjacent C atom ) and is caused by spin- spin coupling.

• Spin –spin coupling is described as the indirect coupling of protons through the
intervening bonding electrons. It occurs because there is some tendency for a
bonding electron pair , to pair its spin with other bonding electron being thus
influenced , the electron will affect the spin of the other bonding electron and
so on to the next proton.

• As resonant absorption continues, the population of the upper state rise to match that
of the lower state. Then there is equal chances of emission and absorption of energy
under resonance condition i.e. transition from low energy state would be as possible
as that from high energy state.

• No net energy change would be detected, when this occurs the sample is said to be
saturated.

• But usually saturation doesn’t occur. This is due to the fact that there are mechanisms
for allowing the nuclei to return to low energy state without emitting radiation .This is
known as relaxation.

• Two mechanisms by which a given nuclei in the excited state can return to the ground
state are referred to as spin-spin relaxation and spin-lattice relaxation.

• Spin-lattice relaxation(Longitudinal relaxation)

• In spin-lattice relaxation, the nuclei in the high energy state relax back to the low
energy state by transferring the energy previously captured to the surrounding or
lattice. Here lattice means the molecular framework which may be either solid ,liquid
or gas.

• Spin-lattice relaxation is also referred to as longitudinal relaxation or T1 and describes

the return to equilibrium in the direction of the magnetic field.

• Nuclei in an NMR experiment are in a sample. The sample in which the nuclei are
held is called the lattice. Nuclei in the lattice are in vibrational and rotational motion,
 which creates a complex magnetic field. The magnetic field caused by motion of
nuclei within the lattice is called the lattice field. This lattice field has many
components. Some of these components will be equal in frequency and phase to the
Larmour frequency of the nuclei of interest.

• These components of the lattice field can interact with nuclei in the higher energy
state, and cause them to lose energy (and return to the lower state).

• The energy that a nucleus loses increases the amount of vibration and rotation within
the lattice (resulting in a tiny rise in the temperature of the sample).

• The relaxation time, T1) (the average lifetime of nuclei in the higher energy state) is
dependent on the magnetogyric ratio of the nucleus and the mobility of the lattice.

• As mobility increases, the vibrational and rotational frequencies increase, making it

more likely for a component of the lattice field to be able to interact with excited
nuclei.

• The simplest NMR experiment is a 90° (π/2) pulse, followed by measurement of the
Free Induction Decay (FID, magnetization in the y' direction of the rotating frame).

• The magnetization will rotate around the Z axis at a rate of 1/Δν, where Δν is the
difference in frequency between the spectrometer pulse frequency, and the Larmor
precession frequency of the nucleus.

• The signal-to-noise ratio (S/N) of an NMR signal is dramatically improved by signal

averaging, the S/N improving as n , where n is the number of signals averaged.

• The fastest way to obtain an NMR signal is to detect the signal following a strong RF
pulse applied at the resonance frequency; this signal is the FID.

• FT NMR
• In pulsed technique, the spectrum obtained will be time domain. The transform of this
domain to ν (frequency) domain is carried out mathematically by Fourier transform.
For this reason, pulsed NMR is usually called Fourier transform NMR (FTNMR). An
entire spectrum can be recorded, computerised and transformed in a few seconds,
repetition every two seconds giving 20 times signal enhancement.

• In a continuous wave NMR spectrometer (CWNMR), the radiofrequency source is

kept at a constant value (60MHz) and Bo is varied .As the field strength increases,
the precessional frequency of each proton increases until resonance with the 60MHz
source takes place(FIELD SWEEP).

• The spectrum is a series of peaks plotted on abscissa that corresponds to variations in

field strength or frequency, but this takes much time.

• FTNMR is a pulse technique (short duration often microseconds).In FTNMR, the

sample is irradiated with a strong pulse of RF energy containing all frequencies over
the 1H range. The protons in each environment absorb their appropriate frequencies
from the pulse (duration 10 microseconds). When the pulse is switched off, the nuclei
undergo relaxation processes and re-emit the absorbed energies and coupling
energies.

• The energy is emitted simultaneously as a complex interacting pattern ,which decays

rapidly .This decaying emission signal is called FREE- INDUCTION DECAY(FID).
It is a time domain function. Fourier transformation is a mathematical process to
convert time domain spectrum into a frequency domain spectrum.
 NMR signal is collected in the Time – domain But, we prefer the frequency domain.

• Fourier Transform is a mathematical procedure that transforms time domain data into
frequency domain.

• The precessing magnetization can be detected to give a signal which oscillates at the
Larmor frequency – the free induction signal. This signal will eventually decay away
due to the action of relaxation; the signal is therefore often called the free induction
decay or FID. The question is how we turn this signal, which depends on time, into
the spectrum, in which the horizontal axis is frequency. This conversion is made using
a mathematical process known as Fourier transformation. This process takes the time
domain function (the FID) and converts it into a frequency domain function (the
spectrum).
• Advantages

• Rapid scanning

• Improved S/N ratio

• high sensitivity

• high resolution

• data processing

• The simultaneous data collection helps one to investigate the spectrum of transient
species such as unstable molecules or intermediates in a chemical reaction for the
analysis of environmental samples.