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•MOLECULAR

SPECTROSCOPY
Spectroscopy
• Study of the Interaction of Electromagnetic
Radiation (Energy) and Matter

• When energy is applied to matter it can be


absorbed, emitted, cause a chemical change
(reaction), or be transmitted.

• Electromagnetic Spectrum:-

Cosmic γ (Gamma) X-Ray


Ultraviolet Visible Infrared
Microwave Radio
THE ELECTROMAGNETIC SPECTRUM

high Frequency (ν ) low


high Energy low

X-RAY ULTRAVIOLET INFRARED MICRO- RADIO FREQUENCY


WAVE

Nuclear
Vibrational
Ultraviolet Visible magnetic
infrared
resonance
2.5 µ m 15 µ m 1m 5m
200 nm 400 nm 800 nm
BLUE RED

short Wavelength (λ ) long


THE SOLAR SPECTRUM
VISIBLE SPECTRUM
(wavelengths of various radiations)

• Violet: 400 - 420 nm


• Indigo: 420 - 440 nm
• Blue: 440 - 490 nm
• Green: 490 - 570 nm
• Yellow: 570 - 585 nm
• Orange: 585 - 620 nm
• Red: 620 - 780 nm
Electromagnetic Spectrum
Type of Frequency Range Wavelength
Type of Transition
Radiation (Hz) Range

gamma-rays 1020-1024 <1 pm nuclear

X-rays 1017-1020 1 nm-1 pm inner electron

ultraviolet 1015-1017 400 nm-1 nm outer electron

visible 4-7.5x1014 750 nm-400 nm outer electron

outer electron molecular


near-infrared 1x1014-4x1014 2.5 µm-750 nm
vibrations

infrared 1013-1014 25 µm-2.5 µm molecular vibrations

molecular rotations, electron


microwaves 3x1011-1013 1 mm-25 µm
spin flips*

radio waves <3x1011 >1 mm nuclear spin flips*

* for energy levels split by a magnetic field


A typical spectrophotometer (or)
spectrometer
Spectroscopy Types:
– Ultraviolet Spectroscopy (UV) – Electronic Energy States
• Use –Conjugated Molecules; Carbonyl Group, Nitro Group

– Infrared Spectroscopy (IR) – Vibrational Energy States


• Use – Functional Groups; Compound Structure

– Nuclear Magnetic Resonance (NMR) – Nuclear Spin States


• Use – The number, type, and relative position of protons
(Hydrogen nuclei) and Carbon-13 nuclei

– Mass Spectrometry (MS) – Hi-Energy Electron Bombardment


• Use – Molecular Weight, Presence of Nitrogen, Halogens
UV Spectroscopy

Observed electronic transitions

σ∗
Unoccupied levels
π∗

Atomic orbital Atomic orbital


Energy n

Occupied levels
π

σ
Molecular orbitals
UV-Spectroscopy
electrons are
UV Spectroscopy

From the molecular orbital diagram, there are several possible


electronic transitions that can occur, each of a different relative
energy:

σ∗
σ σ ∗ alkanes
π∗
σ π ∗ carbonyls

π π ∗ unsaturated cmpds.
Energy
n
n σ ∗ O, N, S, halogens

n π ∗ carbonyls
π

σ
UV transition type
• 1.σ→σ* transitions: for compounds with σ bond
only, high ΔE, short λ (< 200 nm).

• Appears in saturated hydrocarbons with σ orbital and


transition to antibonding σ* or to molecular Rydberg
orbital (higher valence shell orbitals, 3s, 3p, 4s, …),
and involves large ΔE, and small λmax that appears in
far-UV region.

• Eg:- cyclopropane λmax 190 nm.

• cycloalkane λmax 135 nm. (vacum UV)


UV transition type
• 2. n→π* transitions : the excitation of an
electron on an nonbonding orbital, such as
unshared pair e’s on O, N, S,..to an
antibonding π*, usually in an double bond
with hetero atoms, such as C=O, C=S, N=O,
etc. A sym. forbidden and low intensity
transition.

• Ex:- saturated aldehydes and ketones : λmax at


185-300 nm.
UV transition type
• 3.π→π* transitions : for compounds
containing double, triple bonds, or aromatic
rings; a π electron is excited to an
antibonding π* orbital. This is usually a sym.
allowed and high intensity transition.

• Ethylene : absorbs at 162 nm (10000), in


vacuum UV. Extended conjugation lowers,
ΔE, and increase in λmax, if extended beyond
5 double bonds then getting into visible
region.
UV transition type
• 4. n→σ* transitions: excitation from
nonbonding orbital to an antibonding σ*
orbital.

Ex:- CH3OH(vap.) 183 nm (ε 150)


NEt3(vap.) 227 nm (900)
MeI(hexane) 258 nm (380)
Terms describing UV absorptions
1. Chromophores: functional groups that give electronic
transitions.

2.  Auxochromes: substituents with unshared pair e's like OH,


NH, SH ..., when attached to π chromophore they generally
move the absorption max. to longer λ.

3. Bathochromic shift: shift to longer λ, also called red shift.

4. Hysochromic shift: shift to shorter λ, also called blue shift.

5. Hyperchromism: increase in ε of a band.

6. Hypochromism: decrease in ε of a band.


UV Spectroscopy

Chromophores
A. Definition:-

• Remember the electrons present in organic molecules are


involved in covalent bonds or lone pairs of electrons on atoms
such as O or N

• Since similar functional groups will have electrons capable of


discrete classes of transitions, the characteristic energy of these
energies is more representative of the functional group than the
electrons themselves

• A functional group capable of having characteristic electronic


transitions is called a chromophore (color loving)

• Structural or electronic changes in the chromophore can be


quantified and used to predict shifts in the observed electronic
transitions
UV Spectroscopy

I. Chromophores
A. Organic Chromophores
• Alkanes – only posses σ-bonds and no lone pairs of electrons,
so only the high energy σ  σ* transition is observed in the far
UV

This transition is destructive to the molecule, causing cleavage


of the σ-bond
C C
σ∗

σ C C
UV Spectroscopy

I. Chromophores
A. Organic Chromophores
• Alcohols, ethers, amines and sulfur compounds – in the
cases of simple, aliphatic examples of these compounds the n 
σ* is the most often observed transition; like the alkane σ  σ* it
is most often at shorter λ than 200 nm

Note how this transition occurs from the HOMO to the LUMO

C N
σ∗ CN

C N

anitbonding
nN sp3
C N
orbital

σ CN C N
UV Spectroscopy

I. Chromophores
A. Organic Chromophores
• Alkenes and Alkynes – in the case of isolated examples of
these compounds the π  π* is observed at 175 and 170 nm,
respectively

Even though this transition is of lower energy than σ  σ*, it is


still in the far UV – however, the transition energy is sensitive to
substitution

π∗

π
UV Spectroscopy

I. Chromophores
A. Organic Chromophores
• Carbonyls – n  π* transitions (~285 nm); π  π* (188 nm)

π∗
It has been
determined from
C O
n spectral studies, that
carbonyl oxygen
more approximates
sp rather than sp2 !
π O

σCO transitions omitted for clarity


Chromophor Example Excitation λmax, nm ε Solvent

C=C Ethene π __
> π* 171 15,000 hexane

C≡C 1-Hexyne π __
> π* 180 10,000 hexane

n __
> π* 290 15 hexane
C=O Ethanal
π __
> π* 180 10,000 hexane

Nitromethan n __
> π* 275 17 ethanol
N=O
e π __
> π* 200 5,000 ethanol

Methyl
C-X X=Br bromide n __
> σ* 205 200 hexane
X=I Methyl n __
> σ* 255 360 hexane
Iodide
UV Spectroscopy

I. Chromophore

A. Substituent Effects

General – from our brief study of these general chromophores,


only the weak n  π* transition occurs in the routinely observed
UV

The attachment of substituent groups (other than H) can shift


the energy of the transition

Substituents that increase the intensity and often wavelength of


an absorption are called auxochromes

Common auxochromes include alkyl, hydroxyl, alkoxy and


amino groups and the halogens
I. Chromophores
A. Substituent Effects
General – Substituents may have any of four effects on a
chromophore
• Bathochromic shift (red shift) – a shift to longer λ; lower
energy

• Hypsochromic shift (blue shift) – shift to shorter λ; higher


energy

• Hyperchromic effect – an increase in intensity

• Hypochromic effect – a decrease in intensity

Hyperchromic

ε
Hypsochromic Bathochromic
Hypochromic

200 nm 700 nm
UV Absorptions for some isolate chromophores
UV Spectroscopy

III. Instrumentation and Spectra

A. Instrumentation :-
1. The construction of a traditional UV-VIS spectrometer is very
similar to an IR, as similar functions – sample handling,
irradiation, detection and output are required
2. Here is a simple schematic that covers most modern UV
spectrometers:
log(I0/I) = A
UV-VIS sources I0 I

sample
200 700

detector
λ, nm

monochromator/
reference

beam splitter optics I0 I0


16

14

Molecular 12
Extinction
10
Coefficient(w)

200 220 240 260 280 300 320

wavelength(mu)
APPLICATIONS OF UV AND
VISIBLE SPECTROSCOPY
• UV/Vis spectroscopy is routinely used in the
quantitative determination of solutions of
transition metal ions and highly conjugated
organic compounds.
• Organic compounds, especially those with a
high degree of conjugation, also absorb light in
the UV or visible regions of the
electromagnetic spectrum.
• Thus UV/VIS spectroscopy can be used to
determine the concentration of a solution.
• Applications
• Quantitative determination of
chromophores concentrations in solution
• Impurity determination by spectrum
subtraction
• Determination of reaction kinetics