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What physical phenomena can happen when photon

incident on matter?
Bohr frequency Condition
Decides Photon Absorbed Emission
or Emitted Absorption
𝐸2 𝐸2
𝐸2

ℎ𝜈
ℎ𝜈 𝐸1
𝐸1 𝐸1

∆𝐸 = 𝐸2 − 𝐸1 = ℎ𝜈
• 1 in 107 of the incident photons collide with the
Scattering molecules.

• Stokes Radiation: Low energy due to inelastic

scattering.

• While Anti-Stokes Radiation: High energy due to

inelastic scattering.

• Rayleigh: same energy due to elastic Collision.

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• Raman spectroscopy.
 Spectrometer

 Sources of radiation: Sources of radiation are either monochromatic (narrow

frequency range) or polychromatic (broad frequency range).

 Dispersing Element: The role is to separate wavelengths spatially normally

through diffraction grating.

 Detector: A detector is a device that converts radiation into an electric current

or voltage for appropriate signal processing and display.
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 Transitions of the electron in the hydrogen atom

𝑍 2 𝜇𝑒 4
𝐸𝑛 = −
32𝜋 2 𝜀02 ħ2 𝑛2

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 Absorption and Emission Spectroscopy
 In absorption spectroscopy, the net absorption of incident radiation is monitored
as its frequency or wavelength or (wavenumber) is varied.

 Why net absorption?

 When a sample is irradiated, both absorption and emission at a given frequency

are stimulated, and the detector measures the difference, the net absorption.

 The absorption spectrum of chlorophyll.

 Which EM spectrum? Visible region.

 Note that it absorbs in the red and blue regions,

and that green light is not absorbed.

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 Some Typical Organic Chromophores
Chromophore λmax (nm) εmax(cm2 mol-1) Spin Allowed S0 to S1 Transition Type
C-C <180 1000 σ to σ*
C-H <180 1000 σ to σ*
C=C 180 10000 π to π*
C=C-C=C 220 20000 π to π*
Benzene 260 200 π to π*
Napththalene 310 200 π to π*
Anthracene 380 10000 π to π*
C=O 280 20 n to π*
N=N 350 100 n to π*
N=O 660 200 n to π*
C=C-C=O 350 30 n to π*
C=C-C=O 220 20000 π to π*

𝜀= 20 2
10 𝑑 (area of cross section)
𝑑 − 𝑆𝑖𝑧𝑒 𝑜𝑓 𝑡𝑦𝑝𝑖𝑐𝑎𝑙 𝑜𝑟𝑔𝑎𝑛𝑖𝑐 𝑐ℎ𝑟𝑜𝑚𝑜𝑝ℎ𝑜𝑟𝑒𝑠 6
 Molecular Dimensions and Time Scale

 Typical organic molecule size? 0.2-0.6 nm

 Photon takes 33 pico second to travel 1 cm. How to calculate it?

 Blue photon 400 nm takes femto second (interaction time) to interact with a
point. How to calculate it?

 How rapid electron transition occurs?

 We need to first calculate the speed of the electron, for that determine from
bohr orbit, equating energy and centrifugal force. Once speed is calculated,
then calculate the time taken for covering distance of 0.1 nm, which will come
around 1 femto second.

 Thus femto second is the upper limit for any chemical events.

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 Time Scale

 Electronic motion, electron orbital jumps, electron transfer and proton

transfer: Femto second.

 Vibrational motion, weak bond cleavages: Pico seconds

 Rotational and translation motion of molecules , strong bond cleavages, spin-

orbit coupling: Nano to Pico seconds.

 Ultrafast Chemical reactions: Micro second.

 Fast Chemical reactions: From 1 second to 1000 seconds.

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 Beer-Lambert Law
 It is found empirically that the transmitted intensity I varies with the length, L,
of the sample and the molar concentration, [J], of the absorbing species J in
accord with the Beer–Lambert law

𝐼 = 𝐼0 10−𝜀 𝐽 𝐿

 where 𝐼0 is the incident intensity. The quantity ε (epsilon) is called the molar
absorption coefficient.

 The molar absorption coefficient depends on the frequency of the incident

radiation and is greatest where the absorption is most intense. Its dimensions
are 1/(concentration × length), and it is normally convenient to express it in cubic
decimetres per mole per centimetre (dm3 mol−1 cm−1); in SI base units it is
expressed in metres-squared per mole (m2 mol−1).

 What does unit of ε (epsilon) indicate about it physical meaning?

 The latter units imply that ε may be regarded as a (molar) cross-section for
absorption and that, the greater the cross-sectional area of the molecule for
absorption, the greater is its ability to block the passage of the incident
radiation at a given frequency.
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 The spectral characteristics of a sample are commonly reported as the
transmittance, T, of the sample at a given frequency:

𝐼
𝑇=
𝐼0

 The absorbance, A, of the sample:

𝐼0
𝐴 = log
𝐼

 If the transmittance is 0.1 for a path length of 1 cm (corresponding to a 90 per

cent reduction in intensity), then it would be (0.1)2 = 0.01 for a path of double
the length (corresponding to a 99 per cent reduction in intensity overall).

 The two quantities are related by A = −log T (note the common logarithm) and
the Beer–Lambert law becomes

𝐴=ε𝐽 𝐿

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 Broadening of Spectral Line
 Doppler Broadening: One important broadening process in gaseous samples is
the Doppler effect, in which radiation is shifted in frequency when the source is
moving towards or away from the observer.

The Gaussian shape of a Doppler-broadened spectral line

reflects the Maxwell distribution of speeds in the sample at
the temperature of the experiment.

 Lifetime broadening: It is found that spectroscopic lines from gas-phase

samples are not infinitely sharp even when Doppler broadening has been largely
eliminated by working at low temperatures. This residual broadening is due to
quantum mechanical effects. ∆𝐸∆𝑡 ≥ ℎ
4𝜋
 Lifetime broadening arises from the finite lifetime of an excited state and a
consequent blurring of energy levels.

 Collisional/Pressure broadening: Change in energies of molecules due to

Collisions. 11
Beer-Lambert Law
𝐴=ε𝐽 𝐿

Broadening: Contribution of life time

broadening is in the order of 10-8 ev
compared to room temperature Doppler
broadening in the order of 10-3 ev:

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 What is difference between atomic and molecular
spectroscopy
0.01 kJ mol-1 10 kJ mol-1 103 kJ mol-1

The difference from atomic spectroscopy is that the

energy of a molecule can change not only as a result of
electronic transitions but also because it can undergo
changes of rotational and vibrational state. Molecular
spectra are therefore more complex than atomic spectra.

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Rotational spectrum of the Orion nebula, showing spectral
fingerprints of diatomic and polyatomic molecules present
in the interstellar cloud. (Adapted from G.A. Blake et al.,
Astrophys. J. 315,621 (1987).)

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