General Introduction

Nature of radiation energy and its interaction with matter, frequency, wavelength, Electromagnetic
radiation methods of measuring radiation, Origin of the spectra, law of absorption of light

UV-Visible

Introduction, electromagnetic spectra, Beer Lambert Law, effect of solvents, effect of the structure
equipment, applications on inorganic compounds, production of valid spectrum, standards.
Transition types in organic and inorganic compounds, Single-beam and double-beam spectrometer,
Sample preparation, quantitative analyzes

Infra-red spectroscopy

Origin of Infrared Spectra, Vibration of a Diatomic Molecule, Hooke’s law, The Number of Normal
Vibrations for Each Species, Selection Rules for Infrared and Raman Spectra Group Frequencies
and Band Assignments, Intensity of Infrared Absorption, fingerprint for molecule identification,
identification of the presence (or absence) of functional groups.
Raman spectroscopy

Depolarization of Raman Lines, Intensity of Raman Scattering, Principle of Resonance Raman

Spectroscopy, Resonance Raman Spectra, Theoretical Calculation of Vibrational Frequencies,
Vibrational Spectra in Gaseous Phase and Inert Gas Matrices, Symmetry in Crystals, Vibrational
Analysis of Crystals, The Correlation Method, Lattice Vibrations.

Applications in Inorganic Chemistry.

Diatomic, polyatomic molecule, Metal Cluster Compounds, Compounds of Boron, Compounds of

Carbon, Compounds of Silicon, Germanium, and Other Group IVB Elements, Compounds of
Nitrogen, Compounds of Phosphorus and Other Group VB Elements, Compounds of Sulfur and
Selenium.

NMR spectroscopy

NMR - magnetic properties of nuclei - the number of tweaking and atomic number - get a resonance
- NMR spectrum of the protons, Factors affecting the sites packages - packages fission absorption
and Pascal triangle - NMR spectrum for C, P, F, factors affecting the chemical displacement
(coordination number–electronegativity- oxidation state…)
 Principles of molecular spectroscopy:
Electromagnetic radiation
organic light organic relaxation organic
molecule molecule + h
molecule
(ground state) h (excited state) (ground state)

Electromagnetic radiation has the properties of a particle

(photon) and a wave.

 = distance of one wave

 = frequency: waves per unit time (sec-1, Hz)
c = speed of light (3.0 x 108 m • sec-1)
h = Plank’s constant (6.63 x 10-34 J • sec)
 Quantum: the energy of a photon
c
E = h = 

   E   E  

-rays x-rays UV Vis IR microwaves radiowaves

10-10 10-8 10-6 10-5 10-4 10-2 1 108

short Wavelength () long

high Frequency () low
high Energy (E) low
 Principles of molecular spectroscopy:
Quantized Energy Levels

molecules have discrete energy levels

(no continuum between levels)

A molecule absorbs electromagnetic radiation when

the energy of photon corresponds to the difference in
energy between two states
 organic light organic relaxation organic
molecule molecule + h
molecule
(ground state) h (excited state) (ground state)

UV-Vis: valance electron transitions

- gives information about p-bonds and conjugated systems

Infrared: molecular vibrations (stretches, bends)

- identify functional groups

Radio waves: nuclear spin in a magnetic field (NMR)

- gives a map of the H and C framework

Total energy of Molecules include

vibrational • rotational •
electronic •
Electromagnetic radiation
wavelength measurement units
Common Wavelength Units for Electromagnetic Radiation

Unit Symbol Wavelength (m) Type of Radiation

12−
picometer pm 10 gamma ray

10−
angstrom Å 10 x-ray

9−
nanometer nm 10 x-ray

6−
micrometer μm 10 infrared

3−
millimeter mm 10 infrared

2−
centimeter cm 10 microwave

0
meter m 10 radio
UV-Vis: valance electron transitions

: n  p* R- Bands
C=C chromophoric groups C=O O-N=O

(max ‹ 100 liter/ mole. cm) molar absorptivity R- Bands

K- Band p  p*
styrene, benzaldehyde, or - C= C- C= C - mesityl oxide butadiene conjugated p - system
acetophenone

.)molar absorptivities (  max) liter/mole.cm 10000

B- Bands (Benzenoid) broad absorption band multiple peaks near UV max (230
– 270 nm)
E- Bands (Ethylenic) B-bands E1 and E2 – band
‫‪UV.VIS. Spectrophotometer‬‬
‫‪/ 1‬مصدر اإلشعاع‬ ‫يتكون من ‪:‬‬
‫‪ /2‬المحلل‬
‫‪ /3‬المقدر‬
Cells used in the UV spectrum are
made of silica gel and not made of
glass. Why?
Because the glass is absorbed at
about 300 nm, which leads to
overlap between the absorbers

The comparison cell is used for

solvent until only the sample
absorption is shown
 Visible
tungsten lamp

Ultraviolet
discharged Radiation
hydrogen lamp
source
Beer’s Law: There is a linear relationship between
absorbance and concentration

A=cl A = absorbance
c = concentration (M, mol/L)
l = sample path length (cm)
 = molar absorptivity (extinction coefficient)
a proportionality constant for a specific
absorbance of a substance

Molar Absorptivity,:
ε = A/ c L

I ,I0:(A= log I0/I 

 solvents
Factors upon which solvent selection depends: 
Purity 
Ability to dissolve 
Transparency 
Does not react when exposed to ultraviolet light 
nm Solvent nm Solvent

203 Methanol 190 Acetonitrile

204 Ethanol 191 Water
195 Cyclohexane
237 Chloroform 201 Hexane
257 Carbon
tetrachloride
Electronic spectra of complexes

, [Ni(H2O)6]+2 , [Cu(H2O)6]+2
solution of
Solid K3Fe(CN)6
[Co(NH3)5Cl]Cl2
Colors of Representative Compounds of
the Period 4 Transition Metals
b d f h j

a c e g i
 Electronic spectra of complexes

 The spectra resulting from electronic absorption can be

classified into:
 1 / Charge transmission spectrum This spectrum arises
from transitions between the metal ion orbit M and the
Ligand orbit L- M -L
 2 / The ion spectrum associated with the complex ion,
where the negative or positive ion is linked to another ion
to equal its charge.
 3 / Associated spectrum (Legend), each Legend has a
distinctive and special spectrum and absorbs the complex
spectrum, usually in the area of UV.
 4 / The spectrum of the associated field (Legend) arises
from the transitions between the d-orbit of the metal atom
and those that are inseparable in the associated field and
the rest are known as d-d spectra.
 Ligand spectrum (associated)
 Most organic ligands have their own absorptions and are
usually in the visible and UV spectrum and can be three
types
 1 / (n) as in amines and aldehydes (that is, when some
atoms of molecules have a pair of electrons do not enter
into the bond).
.

 2 /( nπ) such as the group C = O in molecules that

share the binding π occurs at 50,000 cm -1 (i.e in the far
ultraviolet region).
 3 / (ππ) in molecules with double and triple bonds
such as aromatic
Spectrum of ions associated with
the complex
Negative ions (oxygen) such as NO2-, NO3- have the 
ability to absorb light strongly in the UV region.
Other ions such as CrO42- have absorption whose ends 
are located in the visible region.
There are negative ions that absorb in the visible and 
UV regions such as Cl-, SO42-, ClO4-
Charge transmission spectra 
The transfer of charge (electrons) can be from metal to 
Ligand (M  L) (metal oxidation).

Or the transfer of electrons from the Ligand to the 

metal (L  M)
The transfer of the charge from the (ML) metal to the
Ligand

The ligand must be easily reducible and the metal is easy

to oxidize, so the ligand with low vacant orbits facilitates
electron transport from the metal.
Example: 2,2-pyridine-1, 1-phenatroline. (Representing
the Legends)
The metal is easy to oxidize, such as Ti3 +, V2 +, Fe2 +, Cu
+, dark complexes
The transport of the charge from M  L from the metal
to the Ligand
Two reduced transitions are V2 and V1
The transfer of charge from metal
to metal
Here one of the ions works for the ligand metal, and the
compounds in which this kind of transition takes place are
bleak.
KFeIII[FeII(CN)6]

Cs2Au1AuIIICl6
 eg

t2 g

(, HCl- , F- , OH- , SCN- 2O , I- , Br-)Weak

field , High spin

eg

t2 g

Low spin ) NH3 , en , NO2- , CN- , Co )

Storing field ,
Absorption maxima in a visible spectrum have three important characteristics

1. number (how many there are)

This depends on the electron configuration of the metal centre

2. position (what wavelength/energy)

This depends on the ligand field splitting parameter, Doct or Dtet and on the degree
of inter-electron repulsion

3. intensity

This depends on the "allowedness" of the transitions which is described by two

selection rules
 As with other types of scientific data, the information extracted
from a UV-visible spectrum can be conveniently summarized in a
table which should accompany the labeled (name, date,
compound, solvent, concentration) spectrum you tape into your
notebook (e.g., for the spectrum in Figure 10 recorded in a 1.0 cm
path length cell):
For example, octahedral [Ti(OH2)6]3+ has a center of
symmetry and thus has a low extinction coefficient (~4.5 cm-
1·M-1) because the transition is symmetry forbidden. However,
no spin flip results, so the transition is spin allowed. Symmetry
and spin allowed transitions typically have extinction
coefficients greater than 1000 cm-1·M-1. As a result of the
symmetry selection rule, octahedral complexes generally have
extinction coefficients between 1 and 100 cm-1·M-1.
Systems with more than one d electron present additional
complexities. For example, in high spin d5 [Mn(OH2)6]2+, each
of the t2g and eg orbitals is occupied by one electron.
Accordingly, d-d transitions are both spin and symmetry
forbidden, and solutions of Mn(II) appear as a very pale pink
colour with extinction coefficients less than 0.1 cm-1·M-1.
The example of [Mn(OH2)6]2+ is still somewhat simplistic,
however, for a multi-d electron system.
Despite the added complexity of electronic states,
we can still make use of UV-visible spectra to
assign coordination geometries by drawing on past
precedent in the literature. For example,
[Co(OH2)6]3+ is a d6 system which is low spin
with three possible electronic states, designated as
1A1g, 1T1g, and 1T2g. Consequently, two
transitions are observed in its UV-visible spectrum
(Figure 12(b) where X = H2O).4 Now, if we
replace two of the “X” ligands with a different
ligand “Y”, two possible geometric isomers result,
cis-[CoX4Y2] and trans-[CoX4Y2].
An example of a multi-d electron system for which
UV-visible transitions can be more easily described
is square planar d8 (e.g., Ni2+) ML4 complexes. As
shown in Figure 13, three spin-allowed transitions
are theoretically possible. In practice, ν1 is often the
only band that can be observed in the visible region;
this is quite useful from the point of view of crystal
field theory since ν1 = Δ in this system. The ν2 and
ν3 bands are higher in energy (shorter λ) and are
frequently masked by other high-energy electronic
transitions.
While it is true that d-d transitions are usually the
most prominent and important features of the
electronic spectra of transition metal complexes,
another class of electronic transitions (called charge
transfer or CT transitions) are frequently observed in
the high energy (low wavelength) region of the UV-
visible spectrum.1 Recall that d-d transitions involve
a redistribution of electrons within the d orbitals. CT
transitions generally result when an electron is
transferred between metal and ligand based orbitals,
and usually require more energy than d-d transitions.
Unlike d-d transitions, those involving charge
transfer are fully allowed.
As a result, CT bands often have molar
absorptivity about 1000 times greater than those
for d-d transitions. When these absorptions fall
within the visible range of the spectrum, they
often produce rich colours.1 Thus, colours in
transition metal compounds are not always
associated with d-d transitions. For example, the
permanganate ion, MnO4– (Mn+7, d0) is a deep
purple colour as a result of charge transfer
between filled ligand orbitals and empty d-
 The color that we see is the color that is
not absorbed, but is transmitted. The
transmitted light is the complement of
the absorbed light.

So if red light is mainly absorbed the color is

green; if green light is mainly absorbed, the
color is red. Numbers are nm
 Color of complexes depend on the value of D0 = h = DE

Crystal-field splitting in a series of octahedral chromium(III) complexes.

“red “violet
absorption” absorption”
“looks green” “looks yellow
The effect of ligand on splitting energy
Effects of the metal oxidation state and of ligand identity
on color

[V(H2O)6]2+ [V(H2O)6]3+

[Cr(NH3)5Cl ]2+
[Cr(NH3)6]3+