Spectroscopy

Spectroscopic Techniques
Spectrometers
Spectrum
Spectrometry
 Spectroscopy
Spectroscopy deals with the transitions induced in a chemical species by its interaction with photons of
electromagnetic radiation.

The most important consequence of electromagnetic interaction is that energy is absorbed or emitted by
the matter in discrete amount called quanta.

The spectroscopic techniques are generally employed to measure the energy difference between various
molecular energy levels and to determine atomic and molecular structures.

The instruments used in such studies, called spectrometers – are deviced to measure relative energy that
is emitted, transmitted or reflected in the infrared, ultraviolet or visible regions as a function of
wavelength or wave number.

The spectrum of the molecule is presented as continuous graph obtained by plotting absorbance or
transmittance of electromagnetic radiation as function of wavelength or wavenumber over a particular
range.
Spectrometry, which is quite different from usual spectroscopic techniques, depends upon the absorption
or emission of electromagnetic radiation.
For instance, in Mass Spectrometry the photographic plate is calibrated to measure various value of m/z.
 Electromagnetic radiation

Maxwell (1864) found that electromagnetic radiation is made up two mutually perpendicular sinosoidal oscillating electric
And magnetic field vectors are represented by E and B respectively:

In spectroscopic studies, the effects associated with the electrical component of the electromagnetic wave are important.

In most branches of spectroscopy the system interacts with the electric field.
However, in case of magnetic resonance spectroscopy it interacts with the magnetic field.
Increasing wavelength:
g-ray  X-rays UV rays  Visible light  IR rays  Microwaves  Radiowaves

Increasing Energy:
Radiowaves  Microwaves  IR  Visible UV  X-rays  g-rays
 Interaction of Electromagnetic Radiation with Matter:

When a beam of light interacts with matter, numerous changes occur in both light and matter.

Electromagnetic radiation is characterized by wavelength, l, frequency, n, intensity I0 and direction.

Important changes that may occur -

1)The direction of light can be changed by reflection and refraction.

2) The beam of light can be transformed into other beams by diffraction, double refraction and scattering.

3) If scattering occurs, the scattered light may exhibit the same frequency as incident light.
This type of scattering is referred as Rayleigh Scattering.

4) If the scattered beam exhibits either higher or lower frequency, t is called Raman Scattering or the Raman effect.

5) If the incident beam is plane polarised, the plane polarization may be rotated by passing through the compound.
It is known as optical rotation and is measured by polarimeter.
6) The intensity of incident beam gets reduced or even disappear when pass through the substance. It is
absorption of light.

(a) if there is an exchange of energy between the light beam and the molecules, a pattern of
wavelength of light absorbed with an indication of energy absorbed at each wavelength constitute the
absorption spectra.
Absorption occurs only when the radiation supplying the right packet of energy impinges on matters.

(b) The extent of absorption may depend on the orientation of the plane polarization in the incident
radiation.
This is called dichroism..

© The absorption of radiation causes atom or molecule to be in an excited state. Since the excited are
short lived (10-8 s), the electron may return to its ground state with emission of certain amount of
energy. When this emission of the light is Instantaneous, the phenomenon is known as fluorescence, if
delayed it is called phosphorescence.

(d) If the light absorption produces chemically reactive substances, the process is called photo-
activation and photochemical reaction.
 Molecular Spectra
In molecule, absorption or emission of electromagnetic radiation occurs when an electron makes a transition
between two energy states of the molecules.

In contrast to the atomic spectra which arise from the transition of electron between atomic energy levels,
The molecular spectra arise from three types of transitions viz. rotational, vibrational and electronic transitions.

BORN-Oppenheimer Approximation
Rotational, vibrational, and electronic energy levels

An isolated molecule in space has various forms of energy by virtue of its different kinds of motion
and intramolecular interactions.

Consider different energies with reference to a diatomic molecule.

The molecule possesses transitional energy by virtue of the motion of the molecule as a whole.

It may possess rotational energy due to bodily motion of molecule about an axis perpendicular to the internuclear axis
and passing through centre of gravity of the molecule.
 BORN-Oppenheimer Approximation
Rotational, vibrational, and electronic energy levels

The molecule exhibits vibrational energy due to periodic displacement of the atoms from their equilibrium positions.

It also possess electronic energy since electron associated with each atom and bond are in constant motion.

Electronic energy associated with each transition of an electron from ground energy level to an excite state energy level
of the molecule due to the absorption of a photon of suitable frequency.

Further, molecule exhibits nuclear energy and energy due to nuclear and electron spins.

As a first approximation, the total energy of a molecule can be expressed as the sum of translational,
rotational, vibrational, electron, spin and nuclear energies .

E total = E trans + Erot + Evib + Eel + E spin + E nuclear

It is assumed that the various types of energy associated with different motions of molecule are
independent of one another.
A molecule can have several levels of these different energy energies.

The transitional energy is not quantized whereas all the energies are quantized.

It means that a molecule can exist only in certain discrete electronic, rotational, vibrational,
spin and nuclear states.

The separation between electronic energy levels is usually much larger than those between
vibrational energy levels.

Which, in terns are much larger than those between rotational levels which is much larger
than spin energy levels.
Thus because of much difference in mass between the electron and the nucleus. Thus,
because of approximation, to regard the respective motions as mechanically separable. This
simplification is usually referred to as Born-Oppenheimer Approximation.

It means that we need not consider electron explicitly in the treatment of molecular
vibrations.
 Furthermore,
E el >> E vib  + E rot > E trans

Since the transitional energy is negligibly small, the Born-Oppenheimer approximation can be written as

E total = E rot + E vib + Eel

The time required for an electronic transition is about 10-15 s and energy involved are
about 10 to 50 times greater than for a typical vibrational transition.

The electronic transition are 102 times faster than the vibrational transitions (10-13 s).

The rotational motion interacts with vibrational motion.. However rotation-vibration interaction
are generally very weak.
The energy involved in a typical rotational transition is about 103 times smaller in magnitude than
in a typical vibrational transition.

Thus, separation of rotational motions from vibrational motions represents a good approximation for
vibrations of free molecules.

The time required for rotational transition (about 10-10 s) is higher than for a typical vibrational transition (10-13 s).

The energy due to nuclear and electron spins is negligible.

Energy Level Diagram:
Each electronic state is associated with a series of vibrational energy levels (designated by vibrational quantum number, v)
Each vibrational level is associated with a rotational energy levels (designated by rotational quantum number, j)
as illustrated in following figure:
 Since the frequency of radiation absorbed or emitted depends on the energy difference (DE) between
the two levels involved in transition and this energy difference is different for rotational,
vibrational and electronic energies etc.

Pure rotational spectra of a molecule are observed in microwave region, the vibrational spectra in the infrared region
and the Electronic spectra in the ultraviolet region or visible region of the electromagnetic spectrum.
 Types of Molecular Spectra

Rotational (Microwave) Spectra: These spectra originate from transitions between the rotational energy levels of a
G aseous molecule on the absorption of radiation falling in the microwave region.
Microwave spectra occur in the spectral range of 1 to 100 cm-1.
Rotational spectra are shown by molecules which exhibit permanent dipole eg. HCl, CO, NO, H2O vapor etc.
Homonuclear diatomic molecules (H2, Cl2, N2 etc) and polyatomic molecule (CO2) which
don't possess a dipole moment, don't exhibit microwave spectra.

Vibrational and Vibration-Rotation (Infrared) Spectra: Here transition between vibrational levels within same electronic
level gives rise to vibrational and vibration-rotation spectra in the infrared regions.
The absorptions bands in this region correspond to fundamental vibrational frequencies of the molecules,
interspersed with substantially weaker overtones and combinations involving lower frequency fundamentals.
The energy range involved is 4000 to 667 cm-1 for organic compounds.
IR spectra are shown by molecules when vibrational motion is accompanied by a change in the dipole moment of the molecule.
Electronic ( Ultraviolet and Visible) Spectra:
Transitions between different electronic energy level give rise to electronic spectra in the ultraviolet and visible region.
Since electronic transitions in a molecule are invariably accompanied by vibrational and rotational transitions,
the electronic spectra Of molecule are highly complex. The electronic spectrum of a sample, if studied in gaseous state,
can show rotational-vibrational structure, But this structure is completely wiped out in liquid samples
sothat electronic spectra in the solution are usually broad.

Nuclear Magnetic Resonance (NMR) Spectra:

NMR spectrum is concerned with the study of interaction energy with
spin-active nuclei which have permanent magnetic moments and quantized nuclear spin states.
NMR spectra results from transition induced between the nuclear spin energy levels of the molecule in an applied
Magnetic field. NMR spectra span the radiofrequency regions viz. 5 to 100MHz.
Electron Spin Resonance (ESR) or Elecron Paramagnetic Resonance (EPR) Spectra:
Electron in the free radicals, atoms, ions or molecules (having unpaired electrons) change their spin under the
Influence of applied magnetic field and spectra arising is called ESR or EPR.
Molecules such as NO, O2 and other parmagnetic systems also show ESR spectra. It observed in microwave region viz 2
9.6 GHz. The ESR spectra are complicated by the fact that coupling occurs between the spinning electron and adjuscent
Spinning nuclei sothat the absorption spectra consists of a multiplicity detrmined y number, nature and position
Of coupling nuclei.

Mossbauer ( also called Nuclear Gamma Resonance Fluorescence, NRF) Spectra:

While NMR Spectra result from absorption of low energy photons of frequency around 60 MHz, Mossbauer spectra result
From absorption of high energy g-phtotn of frequency 1013 MHz by the nuclei.
This technique is based on the principle that molecules in gasoeous phase are converted by bombarding with
electron beams accelerated to an energy of 70eV, into parent and daughter fragments which are sorted
into their mass numbers by passing through combination of Magnetic and or /electric fields.
The method has exceptionally high sensitivity because of capability of counting individual ions as
they transfer charge to an electrode.
Photoelectron Spectra (PES).
In PES,a beam of photons of known energy is allowed to fall on the sample and the kinetic energy of the ejected electron
Is measured.
The difference between the photon energy and the excess kinetic energy gives the binding energy of the electron.
PES can be studied either X-ray photon or UV photons. Former is called XPES while later UVPES or UPES spectra.

Raman Spectra:
Here scattering is measured and not absorption of the radiation. An intense beam of monochromatic radiation
In the visible region is allowed to fall on the sample is alloed to fall on a sample and intensity of scattered
Light is observed at the right angle to the incident beam.
When the scattered light has the same frquency as the incident one is called Rayleigh Scattering or
If the scattered light have different frequencies than the incident beam, it is called Raman scattering.
 Selection Rule:
The general statements that decide between which levels transitions will give rise to spectra lines are
referred as selection rule.
It is often possible to decide whether a particular transition is forbidden or allowed. i.e.
Whether transition probability is zero or non zero.

Deduction of selection rule:

Consider the particle in a box system to deduce selection rules. Treat particle to be an electron and balancing charge
Is symmetrically distributed at the mid point of the well.
The dipole moment is given by
m = ey
where y is the distance of the electron from the centre of potential well.
For a transition from n to m that is induced by electromagnetic radiation, the integral

Must be non zero.

For the deduction of selection rule consider the symmetry of the three functions
 Characteristic Features for Absorption or Emission of electromagnetic Radiation
The energy states of the molecule are quantized.
This shows that a change in energy, DE in any of the energy states of the molecules give rise to a photon
or absorb photon of energy DE.
The phenomena is governed Bohr frequency condition, DE = hn

But this condition for absorption or emission of radiation is not absolutely complete since their occurs strong
or weak lines or bands which have different intensities
Also some expected lines don't occur at all that may satisfy Bohr condition.

The main feature is an electromagnetic wave frequency n is generated by an electric dipole oscillating at
frequency .
Hence for a molecule to undergo interaction with electromagnetic radiation and to absorb or emit a photon of
frequency , it must exhibit an oscillating dipole at that frequency

.
Following conditions may be derived under which a photon can be absorbed or emitted beside
satisfying Bohr condition (i.e. DE = hn).

Transition between Electronic States:

In atom or molecule if an absorption or emission of radiation, the dipole moment changes due to
electron redistribution, electronic transition occur.
If there is no net change in dipole moment and electron charge distribution is symmetrical,
transition is forbidden.

Hence different transitions give rise to different spectra and condition of absorption or emission are
different, which depends on electric dipole interaction.

For instance, in case of heteronuclear diatomic molecules, there is strong absorption of light which is
characteristic of the molecule in accordance with
Bohr condition. On the other hand, homonuclear diatomic molecule like N2, O2, H2 don’t s exhibit
pure rotational or vibrational spectra.
Transition Between Rotational States:
A molecule having permanent dipole moment seems to be a fluctuating dipole when it rotates.
However, if a molecule does not posses a permanent dipole moment, there is no fluctuating dipole on rotation.

Thus the molecule which have permanent dipole moment can absorb or emit radiation by making transition between different
Rotational states.
For instances, HCl show pure rotational spectra a while mononuclear diatiomic molecule (N2, H2, O2) don't exhibit it.
 Transition between Vibrational States:
The dipole moment of a molecule may change when bond stretch or bend in vibrating molecule. The
Oscillating dipole makes electromagnetic field to oscillate and
therefore, radiation may be absorbed or emitted.
Thus, the only molecular vibrations which accompanied by a change in dipole moment can absorb or emit radiation.

Consider the carbon dioxide as an example, in which three atoms are arranged linearly with small net positive charge on
carbon and Small negative charge on oxygen:
During the mode of vibration known as symmetric stretch, the molecule alternately stretched and compressed, both C---O
Bonds changing simultaneously;
Plainly the dipole moment remain zero throughout whole motion of the molecule and this particular vibration is thus
‘infrared inactive’.
However, there is another stretching vibration called anti-symmetrical stretch. Here, one bond stretches while other is
compressed and vice versa.
As a result there is periodic alteration dipole moment and the vibration is the infrared active.
Infra-red Inactive
Infra-red active
Infra-red active
Which of the following molecule can show pure rotational spectra and which
Can show pure vibrational spectra?

H2O, HCl, BF3, CO2, CH4, CCl4, C6H6, N2, O2

H2O, HCl exhibit Rotational Spectra

BF3m CO2, CH4m CCL4, C6H6 exhibit pure vibrational spectra

N2, O2 have no permanent dipole moment or changes during vibrations.

Hence these molecule will not show any spectra
 Spectral Band

• A spectral band is characterized by its position in terms of frequency, intensity, shape and width.
• Band position relate to the appropriate energy levels and is easiest to measure.

Band width

• The width (dn1/2) of a spectral absorption band is normally defined in terms of the half-band width,
that is, width of band at half-height.
 Band width

• The width (dn1/2) of a spectral absorption band is normally defined in terms of the half-band width,
that is, width of band at half-height.

• An isolated, stationary and unperturbed molecular system exhibit definite and fixed energy levels
which give rise to sharp spectral lines.

• However, in bulk mater, the varying intermolecular interactions continuously shift the stationary state energy
levels thereby giving rise to line broadening.
• One of the significant reasons for spectral absorption and emissions being observed not as infinitely sharp line
but as both sharp and broad peaks may be instrumental.
• The mechanical slits in spectrometers are not infinitely narrow and also allow a range of frequencies,
instead of a single frequency, to fall on the detector.
This results in blurring of the absorption or emission pattern.
It is however, possible to improve resolving power of the instrument by suitable spectrometer design,
But there is a minimum width inheriant in any atomic or molecular transition known as natural line
width beyond which no instrument however sophisticated will show the band narrowing or sharpening.
The Heisenberg uncertainty principle states that it is impossible to know
simultaneously the exact position and momentum of a particle. That is, the more
exactly the position is determined, the less known the momentum, and vice versa.
 Factors Contributing to Band Width in Vibrational and Rotational Spectra

1. Uncertainty relation and natural line width:

The width of the band (which actually is a contour of a bunch lines) is called natural width and is defined as
the width of the band at half of its height.
The natural line width or life-time broadening of spectral line can be determined by Heisenberg uncertainty
Principle.
According to uncertainty principle, if a system exists in a state for finite time dt, then the energy of that state will be
uncertain to an extent dE i.e.
dE x dt ≥ h/2 = h/4p

where h is the plank’s constant, since dE = hdn, then the natural line width would be
Dn = 1/4pdt

The lowest energy of state of a system is sharply defined, because the system will remain in that state for a an
Infinite time, if left to itself. So,
Dn =α and hence dE = 0
 Factors Contributing to Band Width in Vibrational and Rotational Spectra

The lowest energy of state of a system is sharply defined, because the system will remain in that state for a an
Infinite time, if left to itself. So,
Dn =α and hence dE = 0

The finite lifetime of an excited state and the consequent energy uncertainty gives a breath to the spectral line.

If the typical lifetime of excited vibrational state is taken as 10 -2 s, the value dE so obtained is 10-34/10-2 = 10-32J.

A transition between the ground state and a typical vibrational excited state will have an energy uncertainty
in the associated radiation Frequency of dE/h, i.e.,

Dn = dE/h = h/4phdt = 1/4pdt

Hence the width of a spectral line is inversely proportional to the lifetime of the absorbing system.

Thus any relaxation mechanism which causes the state to have a lesser lifetime will broaden the spectral line,
 Uncertainty relation and natural line width:

The relaxation time defines only the minimum width for the spectral line. Factors which depend on the environment
and also on the molecule or atom itself determine relaxation times.

The uncertainty is extremely small in comparison with the usual radiation frequency of electronic transitions.

So, natural line width is quite negligible in comparison to that caused by the other types of broadening.

Hence the width of the spectral line may be further broadened to observable dimensions ranging between
0.002 to 0.005 nm by other experimental factors.
 Doppler Broadening :

It arises when a molecule being investigated has a velocity relative to the observer or observing instrument (detector).

Doppler broadening is caused by the motion of the radiating atoms as a result of thermal activity.

According to the Doppler effect, the precise frequencies of radiation which are absorbed or emitted by molecules
(or atoms) depend on their component of velocity in the direction of radiation at the time of interaction.

In liquids and gases, the motion of the molecules causes their absorption and emission frequencies to show Doppler shift.

Different molecules will have different values of the observed frequency.

Doppler effect cause the radiation to effectively decreases the wavelength for those atoms which
travel towards the source and somewhat longer wavelengths are observed for atoms moving away from source.

Since the motion of the gas and liquid phases is random, shift to both low and high frequencies occur and hence
Doppler broadening Spectral line is obtained.
 Doppler Broadening :
(i) If the molecule is moving towards the instrument with velocity v, the obaserved
frequency of radiation n by the molecule is

n’ = n(1+v/c) or ( n-n’)/c = Dn/n = -v/c

Where n is the frequency of the radiation field. c is the velocity of the light, Dn is the Doppler broadening.

(ii) If the molecule is moving away from the measuring instrument with velocity v,
the observed frequency of radiation by the molecule is given by

n’ = n(1-v/c) or ( n-n’)/c = Dn/n = v/c

Thus depending upon the direction of motion of the molecules, the observed frequency becomes either
higher or lower than The actual radiation frequency.
 Doppler Broadening :

Doppler broadening of the spectral line of a molecule of Mass M is given by

Dn/n = (2/c) (2kT ln 2/M) 1/2

Now, the Doppler width is of the order

Dn ~ (7 * 10-7 * (T/M) 1/2 * n0

where T is the temperature in Kelvine and M is the mass of the molecule or atom
in amu.
 How can the Doppler broadening be reduced?

(i) Doppler broadening can be reduced by using molecular beams and carrying observations at right angles to the beam.

(ii) Since dn/n is directly proportional to T1/2, spectral line of maximum sharpness can be obtained by
working with cold gaseous samples.

(iii) To produce narrow emission lines, the temperature of the radiating plasma must be kept low. This is done by keeping the
Lamp current low.
 Collison Broadening:
Molecules (or atoms) in gas and liquid phase are in continuous motion.

collision occurs frequently with each other.

Collision causes small changes in ground state energy levels and interfere with vibrational motion,
hence vibrational spectra get Broadened.

An explanation is that
(i) Intermolecular collisions shorten the lifetime of the excited state thereby broadening of the spectral lines.

(i) Inter molecular collisions also perturb the energies of the outer electrons to some extent and hence cause
broadening of the Electronic spectra.

(iii) The broadening width of visible and ultraviolet spectral lines is due to the fact that these spectra largely
deal with transitions between outer electronic shells.

As a result o f molecular collision, the charge clouds of outer electrons are deformed thereby perturbing the
energy levels Of the electrons. The spectral transitions between these perturbed energy levels are thus
broadened.
 Collison Broadening:

In general, molecular interactions, are less severe in gas than liquids

hence gas-phase spectrum should exhibit sharper line than that of the corresponding liquid.

In solids, the motion of the particles are restricted and are less random and solid spectra therefore exhibit often sharp lines.

The fluctuating intermolecular forces in liquid phase are also absent I the solid.

Microwave spectroscopy of gases provides the experimental support for the theory of collision broadening.
Pressure Broadening