CH-442

Photochemistry I

Prof. Jacques-E. Moser

http://photochemistry.epfl.ch/PC.html



 Content

PHOTOCHEMISTRY I

1. Basic principles
1.1 Introduction
1.2 Laws of light absorption
1.3 Radiation and molecular orbitals
1.4 Selection rules
1.5 Light absorption by solids

2. Molecular photophysics
2.1 Excited state's deactivation pathways
2.2 Kinetics of photochemical processes
2.3 Intermolecular energy transfer

3. Photochemical reactions
3.1 Photodissociation
3.2 Light-induced electron transfer

Content (contd)

4. Synthetic organic reactions

4.1 Reactions of ethenes and aromatic compounds
4.2 Photochemistry of carbonyl chromophore
4.3 Photo-oxygenation reactions

5. Polymer photochemistry
5.1 Photo-polymerization and cross-linking
5.2 Photodegradation and stabilization of polymers

6. Natural photochemical processes

6.1 Atmospheric reactions
6.2 Photochemistry of waters and soils
6.3 Natural photosynthesis
6.4 Mechanisms of vision

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1. Basic principles
 1.1 Introduction

Photochemistry (light-induced chemistry)


Chemistry: forming or breaking of chemical bonds and charge transfer within or between
molecules.
Photochemical reactions are processes during which the energy required for their
activation (ΔU‡ ) or their development (ΔGr ) is provided by an electromagnetic radiation.
Activation energies of the order of ΔU‡ = 100 kJ·mol–1 and bond energies of the order
of ΔG = 200-400 kJ·mol–1 imply absorption of photons that should individually carry an
equivalent amount of energy.

Ultraviolet
Ultra-violet Visible Infra-rouge
Infrared

rouge
jaune
Yellow
bleu

Green
vert
Blue

UV A B C NIR

Red
100 200 300 400 500 600 700 800 900 1000 λ / nm
-1
100000 50000 30000 20000 15000 10000 ν / cm
10.0 5.0 4.0 3.0 2.5 2.0 1.7 1.5 1.3 E / eV
E / kJ·mol–1
800 400 300 200 150 100
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Bond energies

Bond ΔH [kJ mol–1] λ [nm] Bond ΔH [kJ mol–1] λ [nm]

H–H 436 274 N–N 160 748
C–H 413 290 N=N 631 190
N–H 393 304 N N 941 127
P–H 297 403 N–O 201 595
C–C 347 345 N–P 297 403
C–O 358 334 O–H 464 258
C–N 305 392 O–S 265 451
C-Cl 397 301 O–Cl 269 445
C=C 607 197 O–O 204 586
C=O 805 149 C–F 552 216
O=O 498 240 C–S 259 461

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Types of photochemical reactions

a) ΔGr < 0 (exergonic reaction, spontaneous)

∆
Light enable for overcoming the activation

barrier or to lower it by acting as a catalyst. ∆
Such reactions are called "photocatalytic" ∆

Example: H 2 + Cl 2 → 2 HCl

b) ΔGr > 0 (endergonic, non spontaneous)

Energy required by the reaction is brought by

light. Light energy is (partially) converted into

chemical energy.


Example:
Natural photosynthesis
hν 1
CO 2 + H 2O ⎯chloroplastes
⎯⎯⎯ →     C6 H12O 6 + O 2 ΔG = 496 kJ ⋅ mol–1
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Functions associated with light

ν
A ⎯h⎯ → B (± ΔG)

a) Light as a reactant
- synthesis of B

- reaction inhibition (photo-stabilization of A)

b) Light as an energy vector

- endergonic formation of B

- energy storage

c) Light as information vector

- optical absorption profile (photography, information storage)

- charge density profile (xerography)

- 3D material profile (photolithography)




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Fundamental laws of photochemistry

Grotthuss-Draper law (1812, 1842)

Light must be absorbed by a chemical substance in
order for a photochemical reaction to take place.

Theodor von Grotthuss John W. Draper

Stark-Einstein law (1908-1913) (1785-1822) (1811-1882)

Also known as the "photo-equivalence law"

For each photon of light absorbed by a chemical
system, only one molecule is activated for a
photochemical reaction.

hc
ΔGmolecule = N A ⋅ hν = N A ⋅
λ

1 Einstein = 1 mol of photons = NA photons Johannes Stark Albert Einstein

(1874-1957) (1879-1955)

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 1.2 Laws of light absorption

Phenomenological (macroscopic) law of absorption

IR IT = I 0 − I A − I R
I0 IT
IT IR
T= transmittance reflectance IA
I0 I0 absorptance
l I0
IT
A = − log ( ) = – logT absorbance
x0 xl I0

Lambert's law I(x) = I 0 ⋅ exp(−α x)

I(x) IT
ln = −α x ln = lnT = –α l
I0 I0
α = absorption constant [cm–1]

Link with the medium's complex refractive index:

⌢
n = n − iκ   [−] κ = absorption coefficient [-]
Johann H. Lambert 4π ⋅ κ (imaginary part of the

(1728-1777) α= refractive index) 13
λ0

Beer-Lambert Law

I0 IT IT
c A = − log = − logT = ε ⋅ c ⋅ l [-]
I0
l c molar concentration [mol l–1]
l optical pathlength [cm]
ε molar decadic extinction coefficient

Example: c = 10–3 M, ε = 104 mol–1 · L · cm–1




⇒ T = 0.01,  A = 2 ⇒ 99% of the light is

absorbed within the first 2 mm of the solution August Beer
(1825-1863)

Superimposition of absorbing systems

Transmittance is multiplicative: Ttot = ∏ Ti

i

Absorbance is additive: Atot = ∑ Ai

i

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Justification of Beer-Lambert law

Initial assumptions
I(x) σ
S - individual molecules totally block light 

within a characteristic cross-section σ
- monochromatic light
dx - molecules do not cast any shadow on

each other (only conceivable if the

I(x+dx) concentration c is very low)

Absorptance of a solution volume S·dx containing n molecules :

−dI I(x + dx) − I(x) n ⋅ σ c ⋅ S ⋅ N A ⋅ dx ⋅ σ

 =   =   =   = c ⋅ σ ⋅ N A ⋅ dx
I(x) I(x) S S
l

1 ∫ I
−  dI  = c ⋅ σ ⋅ N A ⋅ dx ⎯0⎯→  − ln  = c ⋅ σ ⋅ l ⋅ N A
I(x) I0

σ ⋅ NA I
By defining : ε  = σ ⋅ N A ⋅ log(e) = 
2.303
⇒ − log
I0
 = A =  ε ⋅ c ⋅ l

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Absorption by non-continuous media

Absorption and reflexion by a specular (mirror-like) surface

I0 ϕ ϕ IR
I0 = I R + I A + I T
n0 = 1
Rs = IR / I0 specular reflectance
n ≠ 1 IT
I R (n − 1)2 + n 2 ⋅ κ 2
Fresnel law Rs = = at ϕ = 0
I 0 (n + 1)2 + n 2 ⋅ κ 2

1.0

0.8

0.6
Rs

0.4
n = 1.414
0.2 Augustin Fresnel
(1788-1827)
0
0 2 4 6 8 10 12 14 16
κ  [−]
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Absorption by a scattering medium
I0
IRd
Diffuse reflectance I0 = IRd + IA + IT

Schuster-Kubelka-Munk theory
x
I0 IT

l I0 IRd
I(x)
dx
I(x+dx) J
0

Phenomenological extinction constants: IT

1 dI
k [cm −1 ]  absorption    ks→0 = − ⋅ ln
dx I0
{    }−dI = −kI ⋅ 2dx − sI ⋅ 2dx + sJ ⋅ 2dx
dJ = −kJ ⋅ 2dx − sJ ⋅ 2dx + sI ⋅ 2dx

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IT

Kubelka and Kubelka-Munk equations

Kubelka's hyperbolic solutions

1 − Rg (a − b ⋅ coth (b ⋅ 2s ⋅ l))
R= with: Rg = background reflectance
a + b ⋅ coth (b ⋅ 2s ⋅ l) − Rg
k
b a = 1+ b = a2 − 1
T= s
a ⋅ sinh (b ⋅ 2s ⋅ l) + b ⋅ cosh (b ⋅ 2s ⋅ l)

Kubelka-Munk simplified solution

k (1 − R∞ )2
l → ∞   ⇒ F(R∞ ) =   = 
s 2R∞

Absorber homogeneously dispersed in a scattering medium (powder)

k [cm –1 ] = ln(10) ⋅ ε [mol –1 L cm –1 ]⋅ c [mol L–1 ]

(1 − R∞ )2 ln(10)
F(R∞ ) =  = ε ⋅c⋅
2R∞ s
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IT
Integrating sphere for diffuse reflectance spectroscopy

Specular 
 Specular 

light trap white plate

A. Diffuse reflectance B. Total reflectance

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