Module 1, Lecture 4
Spectroscopy
Reference Books:
1. Fundamentals of Molecular Spectroscopy, 4th Edition,
by Colin N. Banwell and Elaine M. McCash
2. Introduction to Spectroscopy, 5th Edition, Donald L.
Pavia, Gary M. Lampman, George S. Kriz
3. Organic Spectroscopy By William Kemp 1
𝒏 → 𝝅∗ Transititon
The excitation of an electron on a nonbonding (lone
pairs) orbital, such as unshared pair electrons on O, N, S
to an antibonding, π* orbital.
Usually in an double bond with hetero atoms, such as
C=O, C=S, N=O etc show this transition.
e.g. Saturated aldehydes and ketones : 𝝀𝒎𝒂𝒙 185-300 nm
A symmetry forbidden and low intensity transition.
2
In carbonyl compounds, two types of transitions take
place, they are:
High energy transitions: 𝒏 → 𝝈∗ Transition (Intense)
𝝅 → 𝝅∗ Transition (Intense)
Low Energy Transition: 𝒏 → 𝝅∗ Transition (Weak)
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Problems:
Q1. Assign types of electronic transitions for the following
compounds.
Acetaldehyde, Benzene, Cyclohexane, Ethanol, Heptane,
Aniline, Butadiene.
Ans.
Q2. Acetaldehyde is having absorption peak at 160 nm, 180
nm and 292 nm. What type of transition is responsible
for each of these absorption?
Ans.
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Transition Probability
Transition probability: Probability of a particular transition
taking place.
As transition probability increases, intensity of transition
increase (High 𝜺𝒎𝒂𝒙 value).
Depends on:
Energy of the transition/incident light.
Orientation of the molecule/material.
Symmetry of the initial and final states.
Angular momentum (spin).
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Allowed Transitions
The transition whose 𝜺𝒎𝒂𝒙 value is more than 104 are
allowed transitions.
𝝅 → 𝝅∗ Transition is allowed.
𝒏 → 𝝅∗ Transition is forbidden.
e.g. Benzophenone, there are two transitions.
252 nm 𝜺𝒎𝒂𝒙 20000 (allowed)
325 nm 𝜺𝒎𝒂𝒙 180 (forbidden)
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Chromophore
Chromophore is a region/group in the molecule,
which is responsible for the absorption of the UV-
Visible radiation.
Responsible for imparting color to the compound
(some times).
Chromophore are groups containing either 𝝅
electrons or both 𝝅 & n electrons
e.g. C=O, C=C, NO2, –COOH, -N=N-, C≡C etc.
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Auxochrome
A functional group that attached to the chromophore
which modifies the ability of the chromophore to absorb
light, altering the wavelength or intensity of the
absorption.
Saturated group containing unshared electrons attached
to a chromophore: changes both intensity and λmax
e.g. OH, NH2, -SH, -Cl, OR, NHR2 etc.
Auxochromes has ability to extend conjugation of
chromophores by sharing its nonbonding electrons
e.g. Benzene absorbs at 255 nm
Aniline absorbs at 280 nm (moves to longer λmax)
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Absorption and intensity shift
Hyperchromic
Hypsochromic Bathochromic
Absorbance
(Blue Shifted) (Red Shifted)
Hypochromic
Wavelength (nm)
400 nm 700 nm
Examples 1.
e.g. R(CH=CH)nR
n=5
100,000
e
n=4
Red shift and
Hyperchromic shift
50,000
can be observed
n=3
200 300 380
Wavelength (nm)
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Examples 2.
UV-Vis. spectra of acetone in hexane and in water
264 nm (Water)
Absorbance
279 nm (Hexane)
Red shifted and
Hypochromic shift
can be observed
Wavelength (nm)
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Examples 3.
4-Nitrophenol in alkaline medium
𝝀𝒎𝒂𝒙 255 nm 𝝀𝒎𝒂𝒙 265 nm
Because negatively charged oxygen delocalizes more
effectively than the unshared pair of electron
Bathochromic shift (Red shift)
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Examples 4.
Aniline in acidic medium (protonation)
Hypsochromic shift (Blue shift)
13
Examples 5. DNA at different temperatures
At 90 ºC
Absorbance
At 40 ºC
Wavelength (nm)
Double strand DNA absorbed less strongly than denatured DNA due to the
stacking interactions between the bases. On denaturation, the bases are
exposed thereby showing increased interaction.
Hyperchromic shift 14
Examples 6.
Pyridine: 𝝀𝒎𝒂𝒙 = 𝟐𝟓𝟕 𝒏𝒎, 𝜺𝒎𝒂𝒙 : 2750
2-Methylpyridine: 𝝀𝒎𝒂𝒙 = 𝟐𝟔𝟎 𝒏𝒎, 𝜺𝒎𝒂𝒙 : 3560
Examples 7.
Biphenyl: 𝝀𝒎𝒂𝒙 = 𝟐𝟓𝟎 𝒏𝒎; 𝜺𝒎𝒂𝒙 : 19000
2-Methylbiphenyl: 𝝀𝒎𝒂𝒙 = 𝟐𝟑𝟕 𝒏𝒎; 𝜺𝒎𝒂𝒙 : 10250
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Effect of Solvent
Polar excited state
Polar solvent
𝝅 → 𝝅∗ transition
Neutral ground state
Polar solvent will only interact with the polar excited
state and stabilize it. Hence, absorption shifts to longer
wavelength.
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Effect of Solvent
Neutral excited state
Polar solvent
𝒏 → 𝝈∗ transition
Polar ground state
The ground state lower its energy due to solvation with
polar solvents. Hence, the absorption shifts to shorter
wavelength.
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Effect of Solvent
As the solvent polarity
increases:
𝝅 → 𝝅∗ band shifts to
Longer 𝝀𝒎𝒂𝒙
𝒏 → 𝝅∗ band shifts to
Shorter 𝝀𝒎𝒂𝒙
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Example.
Influence of solvent on the UV λmax and εmax of the
n p* and p p* excitation of 4-methylpent-3-en-
2-one.
Solvent p p* n p*
n-hexane 230(12,600) 327(98)
ether 230(12,600) 326(96)
ethanol 237(12,600) 315(78)
water 245(10,000) 305(60)
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Solvent selection
Should not absorb in UV region
Solvents should not contain conjugated systems: most
preferred
Solvent should not interact with solute (Non polar solvent -
does not form H-bonding).
Common solvents used in UV-Vis. spectroscopy
Solvent Minimum wavelength for 1 cm cell, nm
Water, Acetonitrile 190
Cyclohexane 195
n-Hexane 201
Methanol 205
95% Ethanol 205
1,4-Dioxane 215
Methylenedichloride 220
Chloroform 240 20