Electronic Excitation by UV/Vis Spectroscopy :

UV: Radio waves:

X-ray: IR:
valance Nuclear spin states
core electron molecular
excitation electronic (in a magnetic field)
vibrations
excitation
 Spectroscopic Techniques
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

The wavelength and amount of light that a compound absorbs depends on
its molecular structure and the concentration of the compound used.

The concentration dependence follows Beer’s Law.

A=ebc
Where A is absorbance (no units, since A = log(P0 / P )
e is the molar absorbtivity with units of L mol-1 cm-1
b is the path length of the sample - that is, the path length of the cuvette in
which the sample is contained (typically in cm).
c is the concentration of the compound in solution, expressed in mol L-1
 Characteristics of UV-Vis spectra of
Organic Molecules
• Absorb mostly in UV unless highly
conjugated
• Spectra are broad, usually to broad for
qualitative identification purposes
• Excellent for quantitative Beer’s Law-
type analyses
• The most common detector for an
HPLC
Molecules have quantized energy levels:
ex. electronic energy levels.
hv
energy

energy
}
= hv
Q: Where do these quantized energy levels come from?
A: The electronic configurations associated with bonding.

Each electronic energy level

(configuration) has
associated with it the many
vibrational energy levels we
examined with IR.
 Broad spectra

• Overlapping vibrational and rotational

peaks
• Solvent effects
Ethane C C

 
hv

 

 
H HH

H
H
C C
H max = 135 nm (a high energy transition)

Absorptions having max < 200 nm are difficult to observe because

everything (including quartz glass and air) absorbs in this spectral
region.
  
C C  
hv
= hv
=hc/
 
 
 
Example: ethylene absorbs at longer wavelengths:
max = 165 nm e= 10,000
C O
 
 
n hv
n

 
 
n 
The n to pi* transition is at even lower wavelengths but is not
as strong as pi to pi* transitions. It is said to be “forbidden.”
Example:
Acetone: n max = 188 nm ; e= 1860
n max = 279 nm ; e= 15
C C  135 nm

C C  165 nm
H
C O n 183 nm weak

C O  150 nm
n 188 nm
n 279 nm weak

180 nm

C O
A
279 nm


Conjugated systems:
C C

LUMO

HOMO

Preferred transition is between Highest Occupied Molecular Orbital

(HOMO) and Lowest Unoccupied Molecular Orbital (LUMO).
Note: Additional conjugation (double bonds) lowers the HOMO-
LUMO energy gap:
Example:
1,3 butadiene: max = 217 nm ; e= 21,000
1,3,5-hexatriene max = 258 nm ; e= 35,000
Similar structures have similar UV spectra:

O
O

max = 238, 305 nm max = 240, 311 nm max = 173, 192 nm

Woodward-Fieser Rules for Dienes
Homoannular Heteroannular
Parent =253 nm =214 nm
=217 (acyclic)
Increments for: C
Double bond extending conjugation +30
Alkyl substituent or ring residue +5 C C
Exocyclic double bond +5 C
Polar groupings:
-OC(O)CH3 +0
-OR +6
-Cl, -Br +5
-NR2 +60
-SR +30

Homoannular heteroannular acyclic exocyclic

For more than 4 conjugated double bonds:

max = 114 + 5(# of alkyl groups) + n(48.0-1.7n)
Lycopene:

max = 114 + 5(8) + 11*(48.0-1.7*11) = 476 nm

max(Actual) = 474.