CHEM F313: Instrumental Methods of Analysis

Lecture 07
UV-Vis Spectrometry & Fluorescence Spectroscopy
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Outline
α,β-unsaturated ketones/ Aldehydes
Benzenoid and Aromatic systems

Today’s Class
 Charge Transfer Spectra
 Instrumentation
 Dissociation & Re-emission of Energy
 Excitation and deactivation processes
in molecules
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Benzenoid and Aromatic systems
• Electronic spectrum of Benzene shows good fine structure in gas phase, but less pronounced
in solvents
• 3-bands: Intense 184 nm (emax 47000) called E1 or l1
202 nm (emax 7000) called E2 or l2
weak 256 nm (emax 200) called B or l3
• Alkyl groups show red shift due to the hyperconjugative effect (most in p- lowest in o-)
units , nm
Base value for PhCHO 250
Base value for PhCOR 246
These Predictive values Base value for PhCOOH or PhCOOR 230
are more approximate Alkyl, Ring Residue o=3, m=3, p=7
and may vary widely, Hydroxyl –OH, Alkoxyl, -OR o=7, m=7, p=25
MORE than the other O- o=15, m=15, p=80
conjugated systems Chloro, o=0, m=0, p=10
Bromo o=2, m=2, p=15
-NH2 o=13, m=13, p=45
-NHR o=0, m=0, p=73
-NR2 o=20, m=20, p=85
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-NHAc o=20, m=20, p=45
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 Examples

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Charge Transfer Spectra
Examples: Iodine in Hexane is violet in color while in benzene is brown
Tetracyanoethylene (TCNE) in solution of aniline (chloroform) forms a
deep blue colored solution
• Formation of CHARGE-TRANSFER complexes between pairs of
molecules
• Production of two new Molecular Orbitals and consequently to new
electronic transfer opportunities
• Involves a DONOR and an ACCEPTOR (similar to Lewis acid-base pairs)
• Electron–rich HOMO of the donor molecule interacts with electron-
poor LUMO of the acceptor
Charge transfer from electron-rich molecule to electron-deficient
molecule.
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Charge Transfer Spectra
Charge Transfer Donors
NMe2 NH2 OMe

Charge Transfer Acceptors

I2 AlCl3

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Charge Transfer Spectra
 Filled π orbitals in the donor or the nonbonding orbitals overlap with
depleted orbitals in the acceptor.
 Two new molecular orbitals are formed.
 The lower-energy MO for the complex is occupied in the ground
state and transitions from this MO to new upper MO are responsible
for new absorption band.

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Charge Transfer Spectra
The structure of most charge-transfer complexes are visualized as a face-
to-face association on a 1:1 donor:acceptor basis.
+ δ -
δ
I2
Acceptor
Donor
Donor Acceptor
In benzene-iodine case: In aniline-TCNE case:
λmax for benzene is 255 nm λmax for aniline is 280 nm
λmax for molecular iodine in λmax for TCNE is 300 nm
hexane is 500 nm λmax for complex is 600 nm
The charge transfer complex has an intense additional band around 300
nm with a tail in the visible region and modifies the violet color of
molecular iodine to brown
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Charge Transfer Spectra
Charge transfer spectra for transition metal complexes:
• Charge transfer bands are found when electrons move between
orbitals which are mainly of ligand in character and orbitals which are
mainly metal in character.
• These transitions are of high intensity and they depend on the
energies which are related to polarity of the solvent.
• Typically, d-d transitions for transition metals occur in UV-Vis region
• LMCT and MLCT complexes show color arising out of charge transfer

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Charge Transfer Spectra
MLCT: In these type of transitions basically the metal orbitals are
involved that can easily supply their electrons present in the low lying
molecular orbital to the empty π* orbitals of the ligand.

2,2'-bipyridine (bipy), 1,10-

phenanthroline (phen), CO,
CN− and SCN−

• Example of complexes showing these type of transitions are

[Fe(CO)3(bipy)], [Ru(bipy)3]2+, [W(CO)4(phen)] etc.
• In all these cases the π* empty orbital present on the ligand becomes
the receptor of electrons with the introduction of light and the
absorption process.
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Charge Transfer Spectra
LMCT: LMCT transitions take place when electrons are transferred from
the low lying molecular orbital that are principally ligand-disposed to
the orbitals that are primarily metal-based

F-, O2-, N3-

Metal: high ionization

energy and with the
high oxidation states

• The ligands which would favour this would have lower electron
affinity.
• There is no net oxidation-reduction during these transitions as the
excited state has a very short life-time.
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UV-Vis Spectrometry
Instrumentation

Refer to R1 (Instrumental Methods of Analysis by Willard,

Merritt, Dean, Settle; 7th Edition)
Chapter 6 – Full

Important hints
UV-Vis Light Source
Wavelength Selection (Dispersive devices - Basics only)
Cells and Sampling Devices
Detectors
Expect objective questions from instrumentation

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UV-Vis Spectrometry
Instrumentation
Main features
• Sample absorbs a portion of incident radiation
• The remainder is transmitted to detector
• It is changed into an electrical signal
• Displayed after amplification on a meter, chart recorder or
some other type of readout device

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 UV-Vis Spectrometry
Instrumentation
Instruments for measuring the absorption of UV or visible radiation are
made up of the following components
• Sources (UV and visible)
• Wavelength selector (monochromator)
• Sample containers
• Detector
• Signal processor and readout
Sources of UV radiation
• Deuterium source
• The power of the radiation source does not change abruptly over
it's wavelength range
• The electrical excitation of deuterium or hydrogen at low pressure
produces a continuous UV spectrum.
• Both deuterium and hydrogen lamps emit radiation in the range 160
- 375 nm.
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 UV-Vis Spectrometry
Instrumentation
• Quartz windows must be used in these lamps, and quartz cuvettes
must be used, because glass absorbs radiation of wavelengths less
than 350 nm.
Sources of visible radiation
• The tungsten filament lamp is commonly employed as a source of
visible light.
• This type of lamp is used in the wavelength range of 350 - 2500 nm.
• The energy emitted by a tungsten filament lamp is proportional to
the fourth power of the operating voltage

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UV-Vis Spectrometry
Instrumentation
Wavelength selector (monochromator)
• All monochromators contain the following component parts;
 An entrance slit
 A collimating lens
 A dispersing device (usually a prism or a grating)
 A focusing lens
 An exit slit

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 UV-Vis Spectrometry
Instrumentation
• Polychromatic radiation (radiation of more than one wavelength) enters
the monochromator through the entrance slit.
• The beam is collimated, and then strikes the dispersing element at an
angle. The beam is split into its component wavelengths by the grating or
prism.
• By moving the dispersing element or the exit slit, radiation of only a
particular wavelength leaves the monochromator through the exit slit.

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UV-Vis Spectrometry
Instrumentation
Cuvettes
• The containers for the sample and reference solution must be
transparent to the radiation
• Quartz or fused silica cuvettes are required in the UV region.
These cells are also transparent in the visible region.
• Silicate glasses can be used for the manufacture of cuvettes for
use between 350 and 2000 nm.

Detectors
• The photomultiplier tube is a commonly used detector in UV-Vis
spectroscopy.
• It consists of a photoemissive cathode (a cathode which emits
electrons when struck by photons of radiation),
several dynodes (which emit several electrons for each electron
striking them) and an anode.
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 Electronic Transition
The Franck–Condon principle has a well-established semiclassical
interpretation based on the original contributions of James Franck.

Classically, the Franck–Condon

principle is the approximation that an
electronic transition is most likely to
occur without changes in the
positions of the nuclei in the
molecular entity and its environment.

 The resulting state is called a

Franck–Condon state, and the
transition involved, a vertical
transition.
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Dissociation
1.Dissociation
This happens where the equilibrium inter-
atomic distance is just higher than that
required for a bond formation in the
higher energy state
ῡ Continuum Limit = D0" + Eex
Eex is called the excitation energy of one
(or both) of the atoms produced after
dissociation

• Spectrum consists of some vibrational

transitions and a continuum
• D0" + Eex can be obtained from
spectroscopy
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 Dissociation
• This happens when upper electronic
state is UNSTABLE
• Molecule dissociates immediately
after it is excited and products fly off
with resultant kinetic energy of Eex
• Since Ekinetic is not quantized, the
spectrum of the system is a
CONTINUUM. And if we can identify
a lower limit of continuum wave
number, we can find D0" + Eex
precisely

2. Re-emission
This happens when exactly same frequency is radiated
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Excitation and deactivation processes
in molecules
3. Fluorescence:
This happens
• When vibrational energy after the
electronic excitation is lost by
intermolecular collisions
• Energy is lost as heat, but NO Other
radiation is involved = radiation less
transfer process
• When it reaches a lower vibrational
state of the excited state, it emits
radiation of lower energy
• Frequency of fluorescence emission is
• Time gap ~ 10-8 seconds lower than that of the exciting
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Excitation and deactivation processes
in molecules
4. Phosphorescence:
This happens
• When two excited states of
different spin states have
comparable energies
• Some loss of vibrational energy
is already seen
• Intersystem crossing is
kinetically favorable among
states of similar energy,
initiated by collisions etc.
• Radiation is forbidden but
occurs slowly
5. Stimulated emission
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Excitation and deactivation processes
in molecules

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Conclusions
 Charge Transfer Spectra
 Instrumentation
 Dissociation & Re-emission of Energy
 Excitation and deactivation processes in molecules

 Next Class
 Fluorescence Spectroscopy

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