Unit-III: Spectroscopic Techniques

Spectroscopy: It is a general term for the science that deals with

the interactions of various types of radiation with matter
Initially interest was laying on interaction of electromagnetic
radiation with matter
But now-a-days, spectroscopy has been broaden to include
interactions between matter and other forms of energy
Spectrometry & spectrometric methods refer to the measurements
of the intensity of radiation with a photoelectric transducers or
other type of electronic device
Most readily recognizable forms of energy being light and radiant
heat

Molecular Spectroscopy
Light has magnetic and electric components
-oriented at 90
-can be polarized

General Terms
Frequency, , is the number of oscillations of the field that occurs
per second
Wavelength (): The linear distance between any two equivalent
points on successive waves (e.g. successive maxima or minima)
Velocity of propagation (v): frequency in cycles per second
wavelength in meter per cycles
Velocity of radiation depends on the composition of the medium
- Reciprocal of the wavelength in cm1, equal to
Wavenumber ():
k where k is proportionality constant

Electromagnetic Spectrum
X-ray:
core electron
excitation

300 kJ/mol

UV: valance
electronic
excitation

IR: molecular
vibrations

Radio waves:
Nuclear spin states
(in a magnetic field)

170 kJ/mol

Regions of the Electromagnetic Spectrum

Quantum Transitions

Spectroscopic Techniques and

Chemistry they Probe
UV-vis

UV-vis region

bonding electrons

Atomic Absorption

UV-vis region

atomic transitions (val. e)

FT-IR

IR/Microwave

vibrations, rotations

Raman

IR/UV

vibrations

FT-NMR

Radio waves

nuclear spin states

X-Ray Spectroscopy

X-rays

inner electrons, elemental

X-ray Crystallography

X-rays

3-D structure

Spectroscopic Techniques and Common Uses

UV-vis

UV-vis region

Quantitative analysis/
Beers Law

Atomic Absorption

UV-vis region

Quantitative analysis
Beers Law

FT-IR

IR/Microwave

Functional Group Analysis

Functional Group Analysis/
quant

Raman

IR/UV

FT-NMR

Radio waves

X-Ray Spectroscopy

X-rays

Elemental Analysis

X-ray Crystallography

X-rays

3-D structure Anaylysis

Structure determination

Different Spectroscopies
UV-vis electronic states of valence electrons/
d-orbital transitions for solvated transition metals
Fluorescence emission of UV/vis by certain molecules
FT-IR vibrational transitions of molecules
FT-NMR nuclear spin transitions
X-Ray Spectroscopy electronic transitions of core
electrons

Molecular Spectroscopy

UV and UV-Visible Spectroscopy

Absorption

Types of Transitions

In alkenes, only and bonds. So, only , and *, * Mos are present
But amines, ketones, aldehydes & halides have N, O, X and lone pairs on it.
So we need to consider them as non-bonding electrons (n) in the MOs.

Types of Transitions
* and * transitions: high-energy,
accessible in vacuum UV (max <150 nm). Not usually
observed in molecular UV-Vis.
n * and * transitions: non-bonding
electrons (lone pairs), wavelength (max) in the
150-250 nm region.
n * and * transitions: most common
transitions observed in organic molecular UV-Vis,
observed in compounds with lone pairs and multiple
bonds with max = 200-600 nm.
Any of these require that incoming photons match in
energy the gap corresponding to a transition from
ground to excited state.
Energies correspond to a one photon of 300 nm light
are ca. 95 kcal/mol

Example for to *

In alkenes, only and bonds. So, only , and *, * MOs are present

Conjugated Polynenes

Consideration of Non-bonding electrons (n)

Example for a simple enone (ketone + alkene):
*

*;max=218
=11,000

n*;max=320
=100

Here conjugated ketone, We do to consider lone pairs on the O atom

as non-bonding electrons (n) in the MOs.

HowDoUVspectrometerswork?
Matchedquartzcuve9es
Sampleinsolu@onatca.105M.
SystemprotectsPMtubefrom
straylight
D2lampUV
TungstenlampVis
DoubleBeammakesita
dierencetechnique

The Quantitative Picture

Transmi9ance:
T=P/P0

P0
(powerin)

Absorbance:
A=log10T=log10P0/P

P
(powerout)

l (path through sample)

TheBeerLambertLaworBeersLaw:
A=cl
WheretheabsorbanceAhasnounits,sinceA=log10P0/P
isthemolarabsorb@vitywithunitsofLmol1cm1
listhepathlengthofthesampleincm
cistheconcentra@onofthecompoundinsolu@on,expressedinmolL1(orM,molarity)

Organic compounds (many of them)

have UV spectra
Uvscanbeverynonspecic
Itshardtointerpretexceptata
cursorylevel,andtosaythat
thespectrumisconsistentwith
thestructure
Eachbandcanbea
superposiFonofmany
transiFons
Generallywedontassignthe
parFculartransiFons.

Laporte Selection Rule

Selection rules can be relaxed due to:

vibronic coupling
spin-orbit coupling
geometry relaxation during transition

Spin Selection Rule

Shifts in the UV-Visible Spectroscopy

(Blue shift)

(Red shift)

Color Wheel

Why grass and leaves appear in Green color?

Absorption Spectrum of Chlorophyll

Generally, extending conjugation leads to

red shift
particle in a box QM theory; bigger box
Substituents attached to a chromophore that cause a red shift are
called auxochromes
Strain has an effect

max

253239

256

248

Color of Transition Metal Complexes

The Color of [Ti(H2O)]3+

UV-Vis Absorption Spectra of [Ti(H2O)]3+

20,300 cm1

Reddish Violet

Wavelength (nm)

GS
ES
d-d Transition

UV-Vis Spectroscopy of Inorganic Complexes

Same Metal ion with different geometries!

Aqua Complexes of Different Metal ions

Co(III) Complexes shows the effects of Ligands

Co(III) Complexes shows the effects of Ligands

Different Colors!

Charge Transfer (CT) Transitions

Ligand Field Theory (LFT)

Interpretation of UV-Visible Spectra

Transi@onmetalcomplexes;
d,felectrons.
Lanthanidecomplexes
sharplinescausedby
screeningofthef
electronsbyotherorbitals
Oneadvantageofthisisthe
useofholmiumoxidelters
(sharplines)forwavelength
calibra@onofUV
spectrometers.

See Shriver et al. Inorganic Chemistry, 2nd Ed. Ch. 14

IR Spectroscopy Basics

Basic Equation and Isotope Effect

IR Spectroscopy Basics

IR Spectroscopy
Molecular Motions

All of the motions can be described in terms of two types of

molecular vibrations. One type of vibration, a stretch, produces a
change of bond length. A stretch is a rhythmic movement along
the line between the atoms so that the interatomic distance is
either increasing or decreasing

The second type of vibration, a bend, results in a change in bond

angle. These are also sometimes called scissoring, rocking, or "wig
wag" motions

Notethehighwavenumber(highenergy)requiredtoproducethese
mo@ons.Thebendingmo@onsaresome@mesdescribedaswaggingor
scissoringmo@ons

Each of these two main types of vibration can have variations. A stretch
can be symmetric or asymmetric. Bending can occur in the plane of the
molecule or out of plane; it can be scissoring, like blades of a pair of
scissors, or rocking, where two atoms move in the same direction.
Different stretching and bending vibrations can be visualized by
considering the CH2 group in hydrocarbons. The arrows indicate the
direction of motion. The stretching motions require more energy than the
bending ones.

You can see that the lower wavenumber values are consistent with lower energy to
cause these vibrations.
A molecule absorbs a unique set of IR light frequencies. Its IR spectrum is often
likened to a person's fingerprints. These frequencies match the natural vibrational
modes of the molecule. A molecule absorbs only those frequencies of IR light that
match vibrations that cause a change in the dipole moment of the molecule. Bonds in
symmetric N2 and H2 molecules do not absorb IR because stretching does not change
the dipole moment, and bending cannot occur with only 2 atoms in the molecule. Any
individual bond in an organic molecule with symmetric structures and identical
groups at each end of the bond will not absorb in the IR range. For example, in
ethane, the bond between the carbon atoms does not absorb IR because there is a
methyl group at each end of the bond. The C-H bonds within the methyl groups do
absorb.

IR Spectroscopy Basics

Frequency Range:

A typical IR Spectrum of an Org. Compound

O-H stretch appears at 3200-3600, C-H at 3000.

OH

CH

CH3CH2OH

N-H stretch appears at 3200-3500, C-H at 3000

NH

CH

CCstretchappearsat2250,CHat3000

CC

CH

Me

Me

CN stretch appears at 2250, C-H at 3000

CH

CN

CH3CN

C=O stretch appears at 1650-1800, C-H at 3000

CH

C=O

C=C stretch appears at 1650, C-H at 3000

C=C

CH

Alkanes will have only C-H Stretching Frequency

WhatIRpeakswouldyouexpectforthetwomoleculeswiththeformulaC2H6O?

Ethanol

Dimethylether

OH32003400cm1(broad) CH3000cm1
CH3000cm1
CO10601150cm1
CO10601150cm1

IR Spectrum of Octanal
The spectrum for the aldehyde, octanal (CH3(CH2)6CHO), is shown here. The most
important features of the spectrum are carbonyl CO stretch near 1700 cm-1 and the CH
stretch at about 3000 cm-1. If you see an IR spectrum with an intense strong band near
1700 cm-1 and the compound contains oxygen, the molecule most likely contains a
carbonyl group,

IR spectra can be used to identify molecules by recording the spectrum

for an unknown and comparing this to a library or data base of spectra of
known compounds. Computerized spectra data bases and digitized
spectra are used routinely in this way in research, medicine, criminology,
and a number of other fields.
In this exercise you will try to identify the outstanding bands
characteristic of certain bonds and functional groups in the spectra you
examine. You are certainly not expected to identify all the absorption
bands in each IR spectrum at this point in your work.
When you analyze the spectra, it is easier if you follow a series of
steps in examining each spectrum.
Look first for the carbonyl C=O band. Look for a strong band at

1820-1660 cm-1. This band is usually the most intense absorption

band in a spectrum. It will have a medium width. If you see the carbonyl
band, look for other bands associated with functional groups that contain
the carbonyl by going to step 2. If no C=O band is present, check for
alcohols and go to step 3.

If a C=O is present you want to determine if it is part of an acid, an

ester, or an aldehyde or ketone. At this time you may not be able to
distinguish aldehyde from ketone and you will not be asked to do so.
ACID

Lookforindica@onsthatanOHisalsopresent.Ithasabroad
absorp@onnear33002500cm1.ThisactuallywilloverlaptheCH
stretch.TherewillalsobeaCOsinglebondbandnear11001300
cm1.Lookforthecarbonylbandnear17251700cm1.

ESTER

LookforCOabsorp@onofmediumintensitynear1200cm1.There
willbenoOHband..Lookforthecarbonylbandnear17351750cm1

ALDEHYDE

LookforaldehydetypeCHabsorp@onbands.Thesearetwoweak
absorp@onstotherightoftheCHstretchnear2850cm1and2750
cm1andarecausedbytheCHbondthatispartoftheCHOaldehyde
func@onalgroup.Lookforthecarbonylbandaround17401720cm1.

KETONE

TheweakaldehydeCHabsorpFonbandswillbeabsent.Lookforthe
carbonylCObandaround17251705cm1.

If no carbonyl band appears in the spectrum, look for an alcohol O-H band.

ALCOHOL
LookforthebroadOHbandnear

36003300cm1andaCOabsorp@onband

13001000cm1.

near

IfnocarbonylbandsandnoOHbandsareinthespectrum,checkfordoublebonds,C::C,from
anaroma@coranalkene.
ALKENE

Lookforweakabsorp@onnear1650cm1foraC=C.Therewillbe
aCHstretchbandnear3000cm1.

AROMATIC

Lookforthebenzene,C=C,doublebondswhichappearas

mediumtostrongabsorp@onsintheregion16501450cm1.
TheCHstretchbandismuchweakerthaninalkenes.

Ifnoneofthepreviousgroupscanbeiden@ed,youmayhaveanalkane.

ALKANE

Themainabsorp@onwillbetheCHstretchnear3000cm1.Thespectrumwillbesimple
withanotherbandnear1450cm1.

The Possible Modes of Interactions of CO with M

CO Stretching Frequency Depends on e density of M

Structural Assignments using CO Stretching Frequency