Electronic Excitation by UV/Vis Spectros

ElectronicExcitationbyUV/VisSpectroscopy:
Xray:
coreelectron
excitation
UV:
valance
electronic
excitation
IR:
molecular
vibrations
Radiowaves:
Nuclearspinstates
(inamagneticfield)
Thewavelengthandamountoflightthatacompoundabsorbsdependson
itsmolecularstructureandtheconcentrationofthecompoundused.
TheconcentrationdependencefollowsBeersLaw.
A=bc = log I/I0

Where A is absorbance
is the molar absorbtivity with units of L mol-1 cm-1
b is the path length of the sample (typically in cm).
c is the concentration of the compound in solution, expressed in mol L -1
UV Spectrum of Isoprene
=>
- Single bonds are usually too high in excitation energy for most instruments (185 nm)
vacuum UV
most compounds of atmosphere absorb in this range, so difficult to work with.
- Types of electron transitions:
i) , , n electrons
Sigma () single bond electron
Low energy bonding orbital
High energy anti-bonding orbital
Pi () double bond electron
Low energy bonding orbital
High energy anti-bonding orbital
Non-bonding electrons (n): dont take part in any bonds,

neutral energy level.
Example: Formaldehyde
C C
=hv
=hc/
hv
Example:ethyleneabsorbsatmax=165nm=10,000
C O
hv
Thento*transitionisatevenlongerwavelengthsbutisnot
asstrongasto*transitions.Itissaidtobeforbidden.
Example:
Acetone:
n max=188nm;=1860
n max=279nm;=15
C C
135nm
C C
165nm
C O
C O
n 183nm
weak
150nm
n 188nm
n 279nm
weak
188nm
C O
A
279nm
Conjugatedsystems:
C
LUMO
HOMO
Preferred transition is between Highest Occupied Molecular Orbital

(HOMO) and Lowest Unoccupied Molecular Orbital (LUMO).
Additional conjugation (double bonds) lowers the

HOMO-LUMO energy gap:
SimilarstructureshavesimilarUVspectra:
O
O
O
max=238,305nm
max=240,311nm
max=173,192nm
Thevalenceelectronsaretheonlyoneswhoseenergiespermitthemtobe
excitedbynearUV/visibleradiation.
(antibonding)
(antibonding)
n(nonbonding)
(bonding)
Fourtypesoftransitions
*
*
n*
n*
(bonding)
* transition in vacuum UV
n * saturated compounds with non-bonding electrons
~ 150-250 nm
~ 100-3000 ( not strong)
n *, * requires unsaturated functional groups (eq. double bonds)
most commonly used, energy good range for UV/Vis
~ 200 - 700 nm
n * : ~ 10-100
*: ~ 1000 10,000
n*Transitions
Stillratherhighinenergy.between150and250nm.
Notmanymoleculeswithn*transitionsinUV/visregion
max
max
H2O
167
1480
CH3OH
184
150
CH3Cl
173
200
CH3I
258
365
(CH3)2S
229
140
(CH3)2O
184
2520
CH3NH2
215
600
(CH ) N
227
900
n*and*Transitions
MostUV/visspectrainvolvethesetransitions.*are
generallymoreintensethann*.
max
max
C6H13CH=CH2
177
13000*
C5H11CCCH3
178
10000
186
1000
n*
CH3COH
204
41
n*
CH3NO2
280
22
n*
CH3N=NCH3
339
n*
type
O
CH3CCH3
O
Ultraviolet Spectroscopy
200-400 nm photons excite electrons
from a bonding orbital to a *
antibonding orbital.
Conjugated dienes have MOs that are
closer in energy.
A compound that has a longer chain of
conjugated double bonds absorbs light
at a longer wavelength.
=>
Absorption Characteristics of Some Common Chromophores

Chromophore
Alkene
Example
C6H13HC
Solvent
CH2
Alkyne
C5H11C
CH3CCH3
O
Carboxyl
Amido
CH3CH
O
CH3COH
O
Type of
transition
max
n-Heptane
177
13,000
n-Heptane
178
196
225
10,000
2,000
160
*
_
_
n-Hexane
186
280
1,000
16
n*
180
293
Large
12
CH3
Carbonyl
max (nm)
n-Hexane
n*
n*
n*
Ethanol
204
41
n*
Water
214
60
n*
Ethanol
339
n*
CH3CNH2
Azo
H3CN
NCH3
Nitro
CH3NO2
Isooctane
280
22
n*
Nitroso
C4H9NO
Ethyl ether
300
665
100
20
n*
270
12
n*
Nitrate
C2H5ONO2
Dioxane
Most organic spectra are complex

superimposedelectronic and vibration transitions
absorption bands usually broad
detailed theoretical analysis not possible,
effects of solvent & molecular details complicate
comparison
16
- For Compounds with Multiple Chromophores:

If isolated (more than one single bond apart)
- are additive
- constant
CH3CH2CH2CH=CH2
max= 184 max = ~10,000
CH2=CHCH2CH2CH=CH2 max=185 max = ~20,000
If conjugated - shifts to higher s (red shift)

1,3 butadiene:
max= 217 nm ; max= 21,000
1,3,5-hexatriene
max= 258 nm ; max= 35,000
- For Compounds with Multiple Chromophores:
UV Spectral Nomenclature
Blue Shift (Hypsochromic)

Peaks shift to shorter wavelength.
Red Shift (Bathochromic)

Peaks shift to longer wavelength.
Solvent Effects - Intensity

Solventscaninducesignificantchangesintheintensityof
peaks.
HyperchromicIncreaseinabsorptionintensity.
HypochromicDecreaseinabsorptionintensity.
Absorptioncharacteristicsof2methylpyridine
Solvent
max
max
Hexane
260
2000
Chloroform
263
4500
Ethanol
260
4000
Water
260
4000
EthanolHCl(1:1)
262
5200
Solvent effects
-> * transitions leads to more polar
excited state that is more easily stabilized
by polar solvent associations (H-bonds).
The * state is more polar and stabilized
more in polar solvent relative to nonpolar
one, thus in going from nonpolar to polar
solvent there is a red shift or bathochromic
shift (increase in max, decrease in E).
Solvent effects
For n -> * transition, the n state is much more
easily stabilized by polar solvent effects (Hbonds and association), so in going from
nonpolar to polar solvent there is a blue shift
or hypsochromic shift (decrease in max,
increase in E).
n*
methanol
Hypsochromic shift
heptane
Solvent Effects
Auxochrome
Substitutentgroupswhicharenotthemselvesopticallyactiveinthisenergyrange,but
whichdointeractwithotherchromophorestoshiftbothintensityandwavelength.
AbsorptionCharacteristicsofPyridineDerivatives
Derivative
max
max
Pyridine
257
2750
2CH3
262
3560
3CH3
263
3110
4CH3
255
2100
2F
257
3350
2Cl
263
3650
2I
272
400
2OH
230
10000
UVA and UVB

UVA 320nm to 400nm (indirect interaction)
both tans and burns the skin
suppressing the immune system
immediate sunburn reactive oxygen species
UVB 290nm to 320nm (direct interaction)
Skin cancer
Aging
Delayed sunburn
Tanning is based on the control of a complex series of natural

chemical reactions. When exposed to ultraviolet radiation
certain molecules in skin undergo rearrangement. This
rearrangement leads to
formation of Vitamin D from cholesterol,
coloring of skin through the formation of melanins, and
burning or cancer.
Tanning involves the formation of melanin polymers in our skin.

Melanin monomers are already present in the outer layer of the
skin, but in a reduced state. When oxidized upon exposure to
UV, the melanin polymer forms and absorbs light in the visible
and ultraviolet region.
Sun Protection Factor is defined as the ratio of delayed

sunburn on protected skin to unprotected skin, where the
protected skin is covered by 2mg/cm2 of sunscreen.
MED = smallest dose (J/m2) of UVB that

produces a delayed sunburn
SPF 34 should protect you from burning for
thirty-four times the time of unprotected skin.
SPF is based on the physiological response
in the wearer and not based on a direct
comparison of the chemical properties or
dosages of the compounds being used
Active Ingredients
Aminobenzoic acid
15%
Octyl salicylate
5%
Avobenzone
3%
Oxybenzone
6%
Cinoxate
3%
Padimate O
8%
Dioxybenzone
3%
Phenylbenzimidazole sulfonic acid
4%
Homosalate
15%
Sulisobenzone
10%
Menthyl anthranilate
5%
Titanium dioxide
25%
Octocrylene
10%
Trolamine salicylate
12%
Octyl methoxycinnamate
5%
Zinc oxide
25%
(FDA, 1999, p27687)

Electronic Excitation by UV/Vis Spectros

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ElectronicExcitationbyUV/VisSpectroscopy:

A=bc = log I/I0

Sigma () single bond electron

Low energy bonding orbital

High energy anti-bonding orbital

Pi () double bond electron

Low energy bonding orbital

High energy anti-bonding orbital

Non-bonding electrons (n): dont take part in any bonds,

Preferred transition is between Highest Occupied Molecular Orbital

Additional conjugation (double bonds) lowers the

Absorption Characteristics of Some Common Chromophores

Most organic spectra are complex

- For Compounds with Multiple Chromophores:

max= 184 max = ~10,000

CH2=CHCH2CH2CH=CH2 max=185 max = ~20,000

If conjugated - shifts to higher s (red shift)

max= 217 nm ; max= 21,000

max= 258 nm ; max= 35,000

- For Compounds with Multiple Chromophores:

Blue Shift (Hypsochromic)

Red Shift (Bathochromic)

Solvent Effects - Intensity

UVA and UVB

Tanning is based on the control of a complex series of natural

Tanning involves the formation of melanin polymers in our skin.

Sun Protection Factor is defined as the ratio of delayed

MED = smallest dose (J/m2) of UVB that

Phenylbenzimidazole sulfonic acid

(FDA, 1999, p27687)

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