Electronic Excitation by UV/Vis Spectroscopy :

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

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 Beers Law.

A=ebc = log I/I0

Where A is absorbance e 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) s, p, n electrons

Sigma (s) single bond electron

Low energy bonding orbital

High energy anti-bonding orbital

Pi (p) 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

s p
hv

s p

= hv =hc/
p s

p s

Example: ethylene absorbs at max = 165 nm e= 10,000

C O

s p
n
hv

s p
n

p s
n

The n to p* transition is at even longer wavelengths but is not as strong as p to p* transitions. It is said to be forbidden. Example: Acetone: ns max = 188 nm ; e= 1860 np max = 279 nm ; e= 15

C C

s s
p p
H

135 nm
165 nm 183 nm 150 nm 188 nm 279 nm
188 nm

C C

C O

n s p p n s n p

weak

C O

weak

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).

Additional conjugation (double bonds) lowers the HOMO-LUMO energy gap:

Similar structures have similar UV spectra:

O O O

max = 238, 305 nm

max = 240, 311 nm

max = 173, 192 nm

The valence electrons are the only ones whose energies permit them to be excited by near UV/visible radiation. s (anti-bonding) p (anti-bonding) Four types of transitions

n (non-bonding)

ss* pp*
ns*

p (bonding) s (bonding)

np*

s s* transition in vacuum UV n s* saturated compounds with non-bonding electrons n ~ 150-250 nm e ~ 100-3000 ( not strong) n p*, p p* requires unsaturated functional groups (eq. double bonds) most commonly used, energy good range for UV/Vis n ~ 200 - 700 nm n p* : e ~ 10-100 p p*: e ~ 1000 10,000

ns* Transitions
Still rather high in energy. between 150 and 250 nm.
Not many molecules with ns* transitions in UV/vis region
max H2O CH3OH CH3Cl CH3I 167 184 173 258 emax 1480 150 200 365

(CH3)2S
(CH3)2O CH3NH2 (CH3)3N

229
184 215 227

140
2520 600 900

np* and pp* Transitions

Most UV/vis spectra involve these transitions. pp* are generally more intense than np*.
max C6H13CH=CH2 C5H11CCCH3 O CH3CCH3 O CH3COH CH3NO2 CH3N=NCH3 204 280 339 41 22 5 np* np* np* 186 1000 ns* 177 178 emax 13000 10000 type pp* pp*

Ultraviolet Spectroscopy
200-400 nm photons excite electrons from a p bonding orbital to a p* 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 Alkyne

Example

Solvent
n-Heptane n-Heptane

max (nm)
177 178 196 225 186 280 180 293 204

emax
13,000 10,000 2,000 160 1,000 16 Large 12 41

Type of transition pp* pp* _ _ ns* np*

C6H13HC
C5H11C C
O

CH2
CH3

Carbonyl

n-Hexane

CH3CCH3 O CH3CH
Carboxyl n-Hexane

ns* np*
np* np*

O CH3COH O CH3CNH2

Ethanol

Amido

Water

214

60

Azo Nitro Nitroso

H3CN

NCH3

Ethanol Isooctane Ethyl ether

339 280 300 665 270

5 22 100 20 12

np* np*
_

CH3NO2 C4H9NO C2H5ONO2

np*
np*

Nitrate

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) - e are additive - constant
CH3CH2CH2CH=CH2 max= 184 emax = ~10,000

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

If conjugated - shifts to higher s (red shift) 1,3 butadiene: max= 217 nm ; emax= 21,000

1,3,5-hexatriene

max= 258 nm ; emax= 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

Solvents can induce significant changes in the intensity of peaks. Hyperchromic Increase in absorption intensity. Hypochromic Decrease in absorption intensity.
Absorption characteristics of 2-methylpyridine Solvent Hexane max 260 emax 2000

Chloroform
Ethanol Water Ethanol - HCl (1:1)

263
260 260 262

4500
4000 4000 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).

np*
methanol

Hypsochromic shift
heptane

Solvent Effects

Auxochrome
Substitutent groups which are not themselves optically active in this energy range, but which do interact with other chromophores to shift both intensity and wavelength. Absorption Characteristics of Pyridine Derivatives Derivative Pyridine 2-CH3 3-CH3 4-CH3 2-F 2-Cl max 257 262 263 255 257 263 emax 2750 3560 3110 2100 3350 3650

2-I
2-OH

272
230

400
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 Avobenzone Cinoxate Dioxybenzone Homosalate Menthyl anthranilate Octocrylene Octyl methoxycinnamate

15% 3% 3% 3% 15% 5% 10% 5%

Octyl salicylate Oxybenzone Padimate O Phenylbenzimidazole sulfonic acid Sulisobenzone Titanium dioxide Trolamine salicylate Zinc oxide (FDA, 1999, p27687)

5% 6% 8% 4% 10% 25% 12% 25%