Optical properties test

IR and Raman spectroscopy

 Ultraviolet spectroscopy
 NMR spectroscopy
 X-ray spectroscopy
 Infrared spectroscopy
Infrared (IR) spectroscopy measures the bond vibration
frequencies in a molecule and is used to determine the
functional group

The bonds between atoms in the molecule stretch and

bend, absorbing infrared energy and creating the infrared
spectrum.

Symmetric Stretch Antisymmetric Stretch Bend

 selection rules

 Covalent bonds vibrate at only certain allowable

frequencies.
 An electric dipole moment of the molecule
must change during the vibration
Fig 3. spectrum of novolak resin
Raman spectroscopy
Is a light scattering technique, and can be
thought of in its simplest form as a process
where a photon of light interacts with a sample
to produce scattered radiation of different
wavelengths
• Raman spectroscopy is SCATTERING
spectroscopy Scattering involves a
momentary distortion of the electrons distributed
around a molecular bond. Thus, the molecule is
temporarily
Polarized that disappears upon relaxation and
reemission.
• For example, H2 and N2 can be detected
Arrow up = laser photon in; Arrow down = Raman
scattering out
Elastic scattering:
Rayleigh scattering
→ •— • •— • →
Photon in Photon out
No vibration No vibration
If incident photon energy E; vibration energy v,
then
In terms of energy, photon out has energy:
E-v Stokes scattering
E+v anti-Stokes scattering
E Rayleigh scattering
Selection rule for Raman spectrum
Vibration is active if it has a change in
polarizability, α .
Polarizability is the ease of distortion of a bond.
For Raman-active vibrations, the incident radiation
does not cause a change in the dipole moment of the
molecule, but instead a change in polarizability.
In starting the vibration going, the electric field of
the radiation at time t, E, induces a separation of
charge (i.e. between the nuclear protons and the
bonding electrons). This is called the induced dipole
moment, P. (Don’t confuse it with the molecule’s
dipole moment, or change in dipole moment, because
this is often zero).
P = α E
NMR spectroscopy

• NMR is the most powerful tool available

for organic structure determination.
• It is used to study a wide variety of
nuclei:
– 1H
– 13 C
– 15 N
– 19 F
– 31 P
• An electron has a spin quantum number of 1/2 with allowed
values of +1/2 and -1/2
– this spinning charge creates an associated magnetic
field
– in effect, an electron behaves as if it is a tiny bar
magnet and has what is called a magnetic moment
• The same effect holds for certain atomic nuclei
– any atomic nucleus that has an odd mass number, an odd
atomic number, or both also has a spin and a resulting
nuclear magnetic moment
– the allowed nuclear spin states are determined by the
spin quantum number, I, of the nucleus
– a nucleus with spin quantum number I has 2I + 1 spin
states; if I = 1/2, there are two allowed spin states
8.16 ppm

4.82 ppm: the ethylenedioxyl

Fig. spectrum of
PET
4.26 ppm:the ethylenedioxyl group

2.35 ppm: –CH2COO

1.66 ppm –(CH2)2-

Fig. spectrum of
PEA
 UV spectroscopy
Observed electronic transitions
 The lowest energy transition (and most often obs. by UV)
is typically that of an electron in the Highest Occupied
Molecular Orbital (HOMO) to the Lowest Unoccupied
Molecular Orbital (LUMO)
 For any bond (pair of electrons) in a molecule, the
molecular orbitals are a mixture of the two contributing
atomic orbitals; for every bonding orbital “created” from
this mixing (s, p), there is a corresponding anti-bonding
orbital of symmetrically higher energy (s*, p*)
 The lowest energy occupied orbitals are typically the s;
likewise, the corresponding anti-bonding s* orbital is of
the highest energy
 p-orbitals are of somewhat higher energy, and their
complementary anti-bonding orbital somewhat lower in
energy than s*.
 Unshared pairs lie at the energy of the original atomic
orbital, most often this energy is higher than p or s (since
no bond is formed, there is no benefit in energy)
 s*
Unoccupied levels
p*

Atomic orbital Atomic orbital

Energy n

Occupied levels
p

s
Molecular orbitals
 s*
s s* alkanes
p*
s p* carbonyls

p p* unsaturated cmpds.
Energy
n
n s* O, N, S, halogens

n p* carbonyls
p

s
In the manufacture of PLED display using a polymer
it can be stimulated luminescence when a suitable
energy level, they will emit color in the energy
received, based on this ability of the polymer
luminescence Scientists have built PLED screen

PLED display (www.oled.at/Oled-tv-the-next-flat-tv-technology.htm)

 *
*
*
*
n
n
poly(phenylene vinylene) polyfluorene

*
*
n
polyfluorene
 X-ray spectroscopy
nλ = 2 d sin θ
• Constructive interference only occurs for
certain θ’s correlating to a (hkl) plane,
specifically when the path difference is equal
to n wavelengths.