UV-Visible spectroscopy
UV-Visible Spectroscopy
❖ This is the interaction of UV-Vis radiation with matter (or) substance (190 nm
– 750 nm).
❖ It deals with the transitions of electrons between electronic energy levels due
to the absorption of EMR in UV-Vis range.
LUMO
HOMO
Classification of electronic transitions
Allowed and forbidden transitions
Selection rules
❖ Spin selection rule:
The transitions that involve the promotion of electrons without a change in
their spin are allowed transitions.
ΔS=0
Allowed transitions: singlet to singlet; triplet to triplet
Forbidden transitions: singlet to triplet; triplet to singlet
UV-Vis Spectrophotometer
The instrument
UV-Vis Spectrophotometer
Schematic diagram
UV-Vis principle
Beer-Lambert law
❖ The greater the number of molecules capable of absorbing light of a given
wave length, the greater is the extent of light absorption.
❖ The more effectively a molecule absorbs light of a given wavelength, the
greater is the extent of light absorption.
❖ Beer-Lambert law (combination of Beer’s and Lambert’s laws):
• The absorbance value during electronic transitions is directly proportional to
the concentration and the length of the sample
UV-Vis principle
Beer-Lambert law
❖ According Beer-Lambert law, the absorbance versus concentration results a
straight line
(L mol-1 cm-1)
UV-Visible spectrum
❖ UV-Visible spectrum is basically a plot of absobance versus wavelength.
❖ UV-Visible spectrum is broad, why?
UV-Vis spectrum is broad, why?
Frank-Condon principle
❖ Nuclear are havier than electrons in
general. Based on this, the following
rule is stated.
❖ “An electronic transition takes place
so rapidly that the nuclei of a
vibrating molecule can be assumed to
be fixed during the transition”
❖ Therefore, electronic transitions
between the ground and the excited
states take place in a vertical manner.
UV-Vis spectrum is broad, why?
Frank-condon principle
1
Ev = h v + where (v = 0, 1, 2, 3,.....)
2
❖ Vibrational energy at v=0 (zero point
energy) is non-zero
❖ So, vibration of bonds cannot be
frozen out even at low temperatures.
❖ Vibrational transitions from v=0 in the
ground state accompany the electronic
transitions to exicted states
UV-Vis spectrum is broad, why?
Frank-condon principle
❖ Due to many possible transitions, electronic transition consists of a vast
number of lines spaced so closely that the UV-spectrophotometer cannot
resolve them.
❖ Therefore, the result is a broad spectrum
“Chromophore & Auxochrome” concepts
❖ The nuclei of atoms determine the strength with which the electrons are
bound and thus influence the energy spacing between ground and excited
states.
LUMO
HOMO
❖ The characteristic energy of an electronic transition and the wavelength of
radiation absorbed are properties of a group of atoms rather than of
electrons themselves.
“Chromophore & Auxochrome” concepts
❖ Chromophore:
• Chromophore is a group of atoms whch is responsible for the absorption
of UV-Vis radiation and the color of some compounds.
• Chromophores like ethylene, acetylene, dienes etc. contain π-electrons:
They undergo π-π* transitions.
• Chromophores like carbonyls, nitriles etc. contain both ‘n’ and ‘π’
electrons
They undergo π-π* and n-π* transitions
“Chromophore & Auxochrome” concepts
❖ Auxochrome:
• Auxochrome is basically a color enhancing group. It does not absorb any
UV-Vis radiation on itself.
• When it is a substituent on a chromophore, it has the ability to extend the
conjugation by sharing its non-bonding (n) electrons.
• Thus, it can shift the absorption band towards longer wavelengths.
• -OH, -OR, -NH2, –SH, -X etc. are a few examples (groups having lone
pair electrons)
Wavelength and intensity shifts
❖ Bathochromic shift: It is also called a red shift.
• It is a shift towards longer wavelength absorption (due to the addition of
an Auxochrome).
❖ Hypsochromic shift: It is also called a blue shift
• It is a shift towards shorter wavelength absorption (due to the removal of
conjugation from auxochrome).
❖ Hyperchromic shift:
• It leads to the increased intensity.
❖ Hypochromic shift:
• It leads to the decreased intensity
Electronic transitions
Colour of conjugated molecules
❖ β-carotene molecule has a lengthy pi-electron system and its wavelength
maximum is around 480 nm and exhibits an orange colour.
The effect of conjugation on
wavelength absorption
❖ Extension of conjugation leads to the increase in absorption wavelength.
❖ What is an explanation for this?
The effect of conjugation
❖ π→π* transitions are possible in alkenes due to the presence of π-electrons.
❖ As conjugation increases, the energy gap between HOMO and LUMO levels
decreases.
The effect of conjugation
❖ Extension of conjugation leads to the increase in absorption wavelength due to the
decrease in the energy gap between the HOMO and LUMO energy levels.
The Woodward-Fieser rules for
acyclic/cyclic dienes
❖ The absorption wavelength of CH2=CH2: 175 nm
❖ To be able to be detected by a UV-Vis spectrophotometer, the alkene
wavelength must be at least >190 nm.
❖ So, there must be an extended conjugation on CH2=CH2 to fall in UV-Vis
❖ The simplest conjugated molecule is 1,3-butadiene:
❖ By studying a vast number of dienes, Woodward and Fieser devised an
empirical correlation of structural variations that enables us to predict the
wavelength at which a conjugated diene will absorb.
The Woodward-Fieser empirical rules for
acyclic/cyclic dienes
❖ The basic λmax value for only the butadiene in various groups is:
❖ Additional values for each attachment:
Examples
Calculation of wavelength absorption
Examples
Calculation of wavelength absorption
Examples
Calculation of wavelength absorption
Examples
Calculation of wavelength absorption
UV-Vis spectra
UV-Visible Spectroscopy
It is often difficult to extract a great deal of information
from only a UV spectrum itself.
ALWAYS
use in conjunction with
Infrared (IR) and NMR and other
spectroscopic techniques.
