BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture 14
25 Nov 2022
AY 2022-23, Sem-I
Spectroscopy
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Topics to be discussed
7 (14-17) Spectroscopy: (Rotational,
Vibrational, Raman and Electronic):
Absorption and Emission, different
regions of electromagnetic spectrum,
molecular rotation, molecular
vibrations, normal modes, and
rotational transitions accompany
vibrational transitions, Boltzmann
population distribution. Electronic
spectroscopy, Lambert Beer's law
8 (18-20) Coordination Chemistry:
Coordination compounds: Effective
atomic no. concept; Chelates and
isomerism; shapes of d-orbitals,
crystal field theory, octahedral
complexes, spectrochemical series,
CFSE, Effects of crystal field splitting
9 (21-23) Distortion of Complexes, Tetrahedral,
Octahedral, and Square planar
Arrangements : Jahn-Teller distortion:
Effect of geometrical distortions on
stability, stability in other geometries
10 (24-26) Coordination Chemistry, Electronic
spectroscopy and stability aspects:
Electronic spectra of octahedral
complexes, Applications of term
symbols, Thermodynamic and kinetic
aspects of Inorganic complexes during
reactions.
T1: 19.1-19.6, 19.7-19.13  Use the concepts of quantum
mechanics to understand the
20.1-20.8
molecular spectroscopy.
 Concept of bond stretching,
vibration of molecule.
 Identify spectroscopy as an
important tool in modern
science.
R1: p194-200 (SS); p202-214; p222-
224, p232-235  The concept of chelates and
coordination compounds
 Understanding structure and
properties of coordination
complexes in light of various
theories
R1: p214-222  Nature of ligand, idea of
different orbitals and their effect
in inorganic complexes
 Idea of distortion in tetrahedral,
octahedral, and square planar
complexes
R1: p219-222  Spectral nature of inorganic
complexes
R1: p947-960
 Effect of strength and the
R3: p262-264, 380-381, 385-389 symmetry of ligand field on
various energy levels
 Identify the nature of stable and
unstable complexes
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Spectroscopy
Definition
Analysis of electromagnetic radiation absorbed, emitted, or
scattered by atoms and molecules to gather information
In other words
• Analysis of interaction of electromagnetic radiation with
matter
• Atomic and Molecular spectroscopy – What is the
difference?
Molecular spectroscopy involves the change in energy
states for different aspects such as rotation, vibrational
motions of bonds, other perturbations in addition to the
electronic states as in the case of atomic spectroscopy
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Molecular Spectroscopy
What should we study molecular spectroscopy?
To validate the theory that we have learnt so far
To elucidate various chemical and physical
phenomena involved in chemistry
Molecular spectroscopy is more complex and will
also cater more information about bond strengths,
bond lengths, bond angles, energy states etc. and
will be helpful in understanding concentration
changes, kinetics etc. in chemical reactions.

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Consequence of QM treatment
Classical: Energy varies continuously.
Quantum: Energy is quantized.
Our background: PIB, Rotation in 2D, Rotation in 3D,
Vibration, H-Atom.
Application of spectroscopy:
• UV-VIS Spectroscopy: Involving electronic transitions
(π – π*, MLCT etc)
• Intra-red spectroscopy: Uses bond vibration in a
molecule (stretching, bending etc.) and is used to
determine functional group
• NMR spectroscopy: analyzes slight differences of
electron density around H, C etc. nuclei; it is versatile to
identify the structure of new compounds
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Application of Spectroscopy
 Analytical, organic, inorganic use spectroscopy to:
i. identify new compounds
ii. identify intermediates
iii. predict reaction mechanism etc.
 Physical chemistry lab:
i. energy levels and transition,
ii. electric dipole moment, quadrupole moment,
Polarizability,
iii. moment of inertia, NMR, fine structure etc.
 Atomic spectroscopy is the experimental technique
based on which much of QM evolved
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Application in Space-1
Rover — Pragyan

Chandrayaan 2 Large Area Soft X-ray Spectrometer:

Elemental composition of the Moon
Imaging IR Spectrometer: Mineralogy mapping and water-
ice confirmation
Alpha Particle X-ray Spectrometer and Laser Induced
Breakdown Spectroscope: In-situ elemental analysis and
abundance in the vicinity of landing site
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Application in Space-2
The Mars Exploration Rovers were launched with
the goal of searching for and analyzing rock and
soils on Mars. They utilized several spectrometers to
analyze samples.
Mini-TES: miniature thermal emission
spectrometer (examine rock, soil &
atmosphere)
MB: Mossbauer Spectrometer
(examine mineralogy of rocks & soils)

APXS: Alpha Particle X-ray Spectrometer

(analyze elements in rocks & soils)
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Electromagnetic radiation
• Electromagnetic radiation (EMR) includes, in addition to
what we commonly refer to as “light”, radiation of longer
and shorter wavelengths.
• EMR contains both an electric and magnetic component –
plane polarized radiation.
• Electric field of strength of E.
• Magnetic field of strength of H EY

A
X
A
HZ

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EM Radiation Spectrum

Different parts of EMR spectrum can be used to

obtain different kinds of information about the
molecules

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EM Radiation Spectrum
E=h
 = c/, E = hc/

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Interaction of EMR and molecule
Electric/magnetic component of EMR may interact
with the molecule.

How?
• Electric component may interact with the electric
dipole moment of the molecule: Rotational-,
vibrational-, and electronic- spectroscopy.
• Magnetic component may interact with the
magnetic dipole moment of the molecule: NMR-,
EPR- spectroscopy.

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EMR-Molecule Interaction - Processes

E2

Scattering
Energy
Absorption

Absorption

Emission
h Emission h

E1

• Bohr frequency condition h = 

• Wavelength,  = c/, unit is length (in nm etc.)
•Wavenumber, =   c, unit is cm-1
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Schematic of a spectrophotometer
Source:
Grating:
Gunn diode or Klystron (MW)
 A block of reflective material
Mercury arc in quartz envelope (far-IR)
with a grid of parallel lines
Nernst filament (IR)
ruled on its surface
Tungsten lamp (visible)
 disperses the radiation into
Xenon or Deuterium arc lamp (UV)
its frequency components

Detector:
 It responds with an electrical
output proportional to the
intensity of the radiation falling on
it

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Representation of spectrum
100 0

Energy absorbed by

Detector output (%)

 Without any

Sample (%)
sample, detector
output will be
constant
Presence of sample,
detector output will
show a fall in frequency, 0 100
 =(E2 − E1) / h ;
Some energy at this Frequency
frequency will be absorbed
by the sample and will no
longer reach to the detector
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Representation of spectrum

Y-axis :
Intensity of
Absorption/
Transmission/
Emission

X- axis : λ (wavelength) or related

entity such as wavenumber,
frequency etc.

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The intensity of spectral lines
Spectra

line positions line widths Line intensities

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Factors on which absorption depends
Lambert – Beer Law
Absorbance, A = log (I0/I)
Also, A = ε[c]L
Where, I0 and I are the
intensity of the incident and
transmitted radiations,
[c] = concentration
L = path length of the
radiation through the sample
e= molar absorption coefficient,
unit of e = 1/[conc.][length]
Transmittance, T = I/I0 hence, A = - log T
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Some important terminologies
• Resolution: Smallest observable separation
between bands – in terms of wavelength or
frequency.
• Sensitivity: Related to the detector response
• Fourier transform (FT) techniques:
 Used in IR and Raman spectroscopy
 Do not need to use any dispersion element
 It provides simultaneous and almost
instantaneous recording of the whole spectrum
 Fourier transform techniques offer greater
sensitivity and speed.
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Spectral characteristics & transition moments
 For a molecule to be able to interact with the
electromagnetic field and absorb or create a photon of
frequency ν, it must posses, at least transiently, a dipole
oscillating at that frequency.
 This transient dipole is expressed quantum mechanically
in terms of the transition dipole moment, μfi, between
states Ψi and Ψf: where, μ = electric dipole moment
operator. μfi = ∫(Ψf* μ Ψi dτ)
2
Transition probability ∞ ∫(Ψf* μ Ψi dτ)
If μfi is nonzero does the transition contribute to the
spectrum. Therefore, to identify the selection rules, the
condition for which μfi ≠ 0 should be established.
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Spectral characteristics
Selection rules:
Gross – gross feature that molecule must possess – some
molecular properties those can be measured
Specific – which specific transitions are allowed or
forbidden
Line broadening:
Doppler broadening
 Random motion of the particles in a liquid and gaseous
phase relative to the detector leading to shifts to both
high and low frequencies
 This effect is more pronounced for gaseous phase
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Spectral characteristics
Line broadening (contd):
Collision broadening –
 Atoms or molecules in liquid or gaseous phases are in
continual motion and collide with each other
 It causes some deformation of the particles and perturb
the energies of at least the outer electrons that leading to
the broadening
 It is more pronounced for the liquid phase
Thermal broadening – Related to the heat induced motion
of observed species

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Background: Various motions in a molecule

Translational motion: Translational motion will be

like a free particle: KE will vary continuously
z

Rotational motion: Molecule may rotate like a rigid

rotor
Like a weightless rod without
changing its dimensions as a result
of its rotating motion
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Background: Various motions in a molecule

Classical expression of energy for rotational

motion is, j 2
E=
2I
where, j2 = square of the magnitude of angular
momentum

From a quantum mechanical perspective, we have

already obtained the energy of a rigid rotor as

where, J = Angular momentum quantum number

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Background: Various motions in a molecule

Vibrational motion: Bonds in a molecule may

vibrate in different modes, e.g. stretching, bending
etc.
From a quantum mechanical
perspective, we have already obtained
the energy of a harmonic oscillator
(vibrator) as

where, V = vibrational quantum number

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Comparison in energy scale
Consider a simple molecule: C≡O
Expected electronic transition
in CO: 6.5 × 105 cm-1
2 1

Hence, a transition between energy states for different

types of motions/engaging different levels needs different
specific excitation wavelengths of EMR – these will
happen independently
Born-Openheimer Approximation
Ψ = ΨeΨvΨr and E = Ee + Ev + Er
Combined transitions may only happen if the energy
requirement is fulfilled
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Relative energy states

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Discussed topics……

 Introduction of molecular spectroscopy

 EMR-molecule interaction

 Representation of spectrum

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Next class……

 MW/Rotational spectroscopy
 Population at thermal equilibrium
 MW spectroscopy-isotopic effect
 Raman spectroscopy

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