Infra-Red and Uv/Vis Spectroscopy

Infrared Spectroscopy

Infrared Spectroscopy
The quantum mechanical energy levels observed in
IR spectroscopy are those of molecular vibrations
We perceive this vibration as heat
When we say a covalent bond between two atoms is
of a certain length, we are citing an average because
the bond behaves as if it were a vibrating spring
connecting the two atoms
For a simple diatomic molecule, this model is easy to
visualize:

Infrared Spectroscopy
There are two types of bond vibration:

Stretch Vibration or oscillation along the line of the bond

symmetric

asymmetric

Bend Vibration or oscillation not along the line of the bond

scissor

rock
in plane

twist

wag
out of plane

Infrared Spectroscopy
The IR Spectroscopic Process
As a covalent bond oscillates due to the oscillation of the
dipole of the molecule a varying electromagnetic field is
produced

The greater the dipole moment change through the vibration,

the more intense the EM field that is generated

Infrared Spectroscopy
The IR Spectroscopic Process
When a wave of infrared light encounters this oscillating EM field
generated by the oscillating dipole of the same frequency, the two
waves couple, and IR light is absorbed
The coupled wave now vibrates with twice the amplitude
coupled wave

EM oscillating wave
from bond vibration
IR beam from spectrometer

Infrared Spectroscopy
The IR Spectrum
Each stretching and bending vibration occurs with a characteristic frequency
as the atoms and charges involved are different for different bonds
The y-axis on an IR
spectrum is in units of %
transmittance
In regions where the EM
field of an osc. bond
interacts with IR light of
the same
transmittance is low
(light is absorbed)

In regions where
no osc. bond is
interacting with IR
light,
transmittance
nears 100%

Infrared Spectroscopy
The IR Spectrum
The x-axis of the IR spectrum is in units of wavenumbers, , which is the
number of waves per centimeter in units of cm-1
(Remember E = h or E = hc/)

Infrared Spectroscopy
The IR Spectrum
This unit is used rather than wavelength (microns) because wavenumbers
are directly proportional to the energy of transition being observed
chemists like this, physicists hate it
High frequencies and high wavenumbers equate higher energy
is quicker to understand than

Short wavelengths equate higher energy

This unit is used rather than frequency as the numbers are more real
than the exponential units of frequency
IR spectra are observed for the mid-infrared: 600-4000 cm-1
The peaks are Gaussian distributions of the average energy of a transition

The IR Spectrum
In general:
Lighter atoms will allow the oscillation to be faster higher energy
This is especially true of bonds to hydrogen C-H, N-H and O-H
Stronger bonds will have higher energy oscillations
Triple bonds > double bonds > single bonds in energy

Energy/ of oscillation

The IR Spectrum The detection of different bonds

As opposed to chromatography or other spectroscopic methods, the area
of a IR band (or peak) is not directly proportional to concentration of the
functional group producing the peak
The intensity of an IR band is affected by two primary factors:
Whether the vibration is one of stretching or bending
Electronegativity difference of the atoms involved in the bond
For both effects, the greater the change in dipole moment in a given
vibration or bend, the larger the peak.
The greater the difference in electronegativity between the atoms
involved in bonding, the larger the dipole moment
Typically, stretching will change dipole moment more than bending

The IR Spectrum The detection of different bonds

It is important to make note of peak intensities to show the effect of these
factors:
Strong (s) peak is tall, transmittance is low (0-35 %)
Medium (m) peak is mid-height (75-35%)
Weak (w) peak is short, transmittance is high (90-75%)
* Broad (br) if the Gaussian distribution is abnormally broad
(*this is more for describing a bond that spans many energies)
Exact transmittance values are rarely recorded

Infrared Group Analysis

General
The primary use of the IR is to detect functional groups
Because the IR looks at the interaction of the EM spectrum with actual
bonds, it provides a unique qualitative probe into the functionality of a
molecule, as functional groups are merely different configurations of
different types of bonds
Since most types of bonds in covalent molecules have roughly the same
energy, i.e., C=C and C=O bonds, C-H and N-H bonds they show up in
similar regions of the IR spectrum
Remember all organic functional groups are made of multiple bonds and
therefore show up as multiple IR bands (peaks)

II.
5.
Bonds to H

Infrared Group Analysis

A. General
The four primary regions of the IR spectrum
Triple bonds Double bonds

Single Bonds

Fingerprint
Region
O-H
N-H
C-H

4000 cm-1

CC
CN

2700 cm-1

C=O
C=N
C=C

2000 cm-1 1600 cm-1

C-C
C-N
C-O

600 cm-1

Infrared Spectroscopy
1.

Effects on IR bands
Conjugation by resonance, conjugation lowers the energy of a double or triple
bond. The effect of this is readily observed in the IR spectrum:
O
O

1684 cm -1
C=O

1715 cm -1
C=O

Conjugation will lower the observed IR band for a carbonyl from 20-40 cm -1
provided conjugation gives a strong resonance contributor
O
C
H3 C

X=

NH 2

CH 3

Cl

NO 2

1677

1687

1692

1700

O
H 2N

C CH 3

Strong resonance contributor

vs.
O

O
C
CH3

Poor resonance contributor

(cannot resonate with C=O)

cm -1

Infrared Spectroscopy
2.

Effects on IR bands
Steric effects usually not important in IR spectroscopy, unless they reduce the
strength of a bond (usually ) by interfering with proper orbital overlap:
O

CH 3
C=O: 1686 cm-1

3.

C=O: 1693 cm-1

Here the methyl group in the structure at the right causes the carbonyl
group to be slightly out of plane, interfering with resonance

Strain effects changes in bond angle forced by the constraints of a ring will
cause a slight change in hybridization, and therefore, bond strength
O

1815 cm-1

1775 cm-1

1750 cm-1

1715 cm-1

1705 cm-1

As bond angle decreases, carbon becomes more electronegative, as well

as less sp2 hybridized (bond angle < 120)

Infrared Spectroscopy

Effects on IR bands
4. Hydrogen bonding
Hydrogen bonding causes a broadening in the band due to the creation of
a continuum of bond energies associated with it
In the solution phase these effects are readily apparent; in the gas phase
where these effects disappear or in lieu of steric effects, the band appears
as sharp as all other IR bands:
Gas phase spectrum of
1-butanol
Steric hindrance to H-bonding
in a di-tert-butylphenol
OH

H-bonding can interact with other functional groups to lower frequencies

O

C=O; 1701 cm-1

Thermal Occupation of
Molecular Energy Levels
Intensity of a transitions depends on strength and on population ratio
of initial and final states. Probability that energy level Ei occupied is
given by the Boltzmann distribution:

P (E i ) N(E i ) / N0 g(E i )exp(E i / kBT )

where kB is the Boltzmann constant [1.381023 J K1] and g(Ei) is
the degeneracy of Ei (number of quantum states corresponding to Ei).
Population ratio for two energy levels Ei and Ef is

P (E i ) / P (E f ) [g(E i ) / g(E f )]exp (E i E f ) / kBT

At room temperature, kBT = 41021 J (or 2.5 kJ mol1), and is large

compared with rotational energy spacings (hence, many rot. states
populated at room temperature), smaller than vibrational energy
spacings, very much smaller then electronic energy spacings.

Vibrations and Rotations of Molecules:

Infrared & Microwave Spectroscopy
Three types of nuclear motion: translation, rotation, and vibration.
Translation corresponds to particle-in-a-box motion in a macroscopic
box not relevant to molecular spectroscopy.
We consider rotational motion (spectroscopy in MW region) and
vibrational motion (spectroscopy in IR region).

Rotations of Molecules
Rotational motion corresponds to tumbling of molecule in space
(change of angular coordinates relative to fixed, laboratory axes.
Example: diatomic molecule
We can assume that the bond length does not
change. Molecule can be considered
z
rigid as it rotates.

y
x

Rotations of Molecules
Energy depends on moment of inertia:

I Re2

m1m2

m1 m2

is the reduced mass.

Re bond length
Only certain quantized energies

E rot,J

h2
2

J (J 1) hBJ (J 1)

8 I
where J = 0,1,2,
B

h
2

8 I

is the rotational constant

Degeneracy g(EJ) = 2J + 1

Diatomic molecule

Rotations of Molecules
Selection rules: Molecule must have permanent dipole moment
(homonuclear diatomics have no pure rotational spectrum), allowed
changes in J: J = +1.

E
h

h
2

J f (J f 1) J i (J i 1)

(J i 2)(J i 1) J i (J i 1)

8 I
h
8 I
h
2

4 I

(J i 1) 2B(J i 1)

Rotational Spectrum
of a Diatomic Molecule
Emission spectrum from rotationally hot HF molecules

Radioastronomy
Microwave emission spectrum of Orion nebula, showing the presence
of diatomic and polyatomic molecules in the interstellar cloud.

Vibrations of Molecules
We now consider distortions to the bond lengths. Consider potential
energy curve of a diatomic molecule.
Vibrational motion about equilibrium
bond length. For small change R Re,
restoring force is

F k(R Re )
k is the force constant, measures
stiffness of bond, related to strength.
Units of k: J m2, or kg s2.
This force describes a harmonic
oscillator.

Vibrations of Molecules
In classical mechanics, atoms will oscillate about equilibrium separation,
at frequency
1 k

2
Only certain energies in quantum

E vib,v h (v 21 ),

v 0,1,2,...

Note ground state (v=0) does not have

zero energy. Residual energy (1/2)h
is called zero-point energy, consequence
of uncertainty principle.

energy

mechanics:

v=1
v=0
R Re

V(R Re) = (1/2)k(R Re)2

Vibrations of Molecules
Vibrational transitions occur in the infrared spectral region. Strong
absorption observed for v = +1 changes in vibrational quantum number.
Harmonic oscillator only approximate
description of molecular vibration.
True PE curve of molecule shows
dissociation for a diatomic molecule.
PE curve is anharmonic.
Can determine dissociation energy
by summing vibrational spacings.

Vibrations of Molecules
Absorption spectrum of diatomic molecules domonated by
the v=0 v=1 transition. Example: carbon monoxide

Vibrations of Molecules
In polyatomic molecules, several types of vibrational motion possible.
Nonlinear triatomic molecule: Nvib = 3N 6 = 9 6 = 3 modes.

Example: water (H2O) molecule

Vibrations of Molecules
Absorption spectra of gases show rotational fine-structure built upon the
vibrational transitions

Absorption
spectrum
of methane:

stretch
How many vibrational degrees
of freedom for methane?

bend

Vibrations of Molecules
Spectra of larger polyatomic molecules can be useful in identification
of compounds.
Absorption spectrum of ethanol:

Excited Electronic States:

Electronic Spectroscopy of Molecules
Excited molecular electronic states can be described within framework of
molecular orbital theory.
Example: ethylene

Conjugated Systems
Conjugated -bonded system alternating double and single bonds.
Lowest-energy orbital extends over full geometry, resembles standing
wave over full length of molecule. As length of the conjugated system
is increased, wavelengths become longer, and energies shift lower.

Absorption of Light by Molecules with Conjugated Electron Systems

Molecule

Number of C=C Bonds

Wavelength
of Max. Abs.(nm)

C 2H 4

162

C 4H 6

217

C 6H 8

251

C8H10

304

Conjugated Systems: -Carotene and Indigo

Beta-Carotene

Indigo
Absorption spectra of
two dyes:
carotene and indigo

The Fate of Excited Electronic States

What happens to molecules after they absorb radiation?
Some emit photon and return to ground electronic state (but in different
vib.-rot. level). This process is called fluorescence time scale 10 9 s.
Second type of emission occurs much more slowly called
phosphorescence.
Difference in these processes due to spins of the electrons in excited
state.

The Fate of Excited Electronic States

Light absorption does not change spins of electrons remain
antiparallel (called singlet state). Another possible state has spins
parallel (triplet state). Small probability that excited singlet can cross
over to excited triplet. Triplet emits very slowly because spin must
flip back.

The Fate of Excited Electronic States

Radiative and non-radiative
decay pathways for
electronically excited
molecules.

Sensitive Detection of Molecules

Beer-Lambert law for absorption is not the most sensitive way to
detect molecules at low concentration. Concentration depends on
determining ratio of IS and IR accurately. Akin to measuring weight
of captain by measuring captain+ship and ship, and taking difference.
One way to improve detection sensitivity is to use fluorescence.
Signal comes on a zero background. However, method not
applicable to all molecules, only those that fluoresce.

Lasers
Spontaneous and stimulated emission
Laser (light amplification by stimulated emission of radiation))
first demonstrated with visible light in 1960 (T. Maiman)
unique properties of laser light:
monochromatic
collimated
coherent
Requires a pumping mechanism
pump photons
electric discharge
chemical reaction

Examples of Lasers
Fixed wavelength

Diode laser
(used in CDs.
DVDs, and
laser pointers)

Nd:YAG laser

HeNe laser

Variable wavelength
Dye laser

YAG = yttrium aluminum garnet

Introduction to Atmospheric
Photochemistry
Composition of air at earths surface
N2
78.11%
O2
20.95
Ar
0.93
H2O
07%
Structure of atmosphere layered.
Density is low in outer layers. Suns
radiation causes extensive ionization.
Troposphere dynamically unstable
since cooler, denser air above warmer
air at surface.

Photochemistry in the Stratosphere

If molecule absorbs light of photon energy greater than bond energy,
it can dissociate. The fragments are usually highly reactive and lead
to chemical reactions photochemistry.
Consider photodissociation of
oxygen molecule. Absorption
spectrum shows transitions to
vibrational levels of excited
electronic states, as well as
continuous absorption. The latter
is transition to repulsive
excited electronic state.

250 nm

wavelength (nm)

192 nm

Photochemistry in the Stratosphere

Potential energy curves of the electronic states of O2.

UV solar radiation
O2 is photodissociated

O2 h 2 O

Photochemistry in the Stratosphere

Formation and destruction of ozone in the stratosphere

O2 h 2 O

O3* = energized molecule

O O2 O3*
O3* M O3 M

M = another molecule (usually N2 or O2)

Ozone in the stratosphere absorbs 200-350 nm solar radiation, protects

life on earths surface from damaging UV radiation.
Catalytic destruction of ozone by chlorofluorocarbons (CFCs), e.g. CCl2F2.
CFCs inert in troposphere but photodissociated in the stratosphere:

CCl2F2 h CCl2F Cl
Cl O ClO
ClO O3 Cl 2 O2

The Greenhouse Effect

Sun illuminates earth with visible radiation. Earth radiates IR radiation
back into space. Earths temperature results from balance between
energy input and loss.

Atmospheric gases
(e.g. CO2, CH4)
absorb IR radiation
and reduce amount
of energy radiated
back into space.

The Greenhouse Effect

Increase in concentration of atmospheric gases, especially CO 2 from
fossil fuel burning, is leading to increase in global temperature.

Monthly CO2 concentrations at Mauna Loa, Hawaii