ELECTRONIC EXCITED STATES

p
photon of
suitable
energy The excited state is a NEW CHEMICAL
SPECIES with its own chemical and
A + hν A*
A h i l properties
physical ti
ground electronically
state excited state

electronically
photochemical reactions
excited states

light
UV-Vis

electronic ground state thermal reactions

 FORMALDEHYDE

lowest excited
ground state
state
t t
1A
1 3A (n→π*)
2

H ((−))
C O H C
O
H H (+)

energy 0 + 76 kcal/mol
geometry planar pyramidal
magnetism
ti di
diamagnetic
ti paramagnetic
ti
dipole moment 2.3 D 1.3 D
rCO 1 22 Å
1.22 1 31 Å
1.31
νCO 1745 cm-1 1180 cm-1
lif ti
lifetime ∞ < 10-33 s
 N Ru(bpy)
( py)2((CN))2
N N
Ru N
C lowest excited
N C
ground
d state t t
state
N 3MLCT (Ru→bpy)

energy 0 + 50 kcal/mol
geometry slightly different
magnetism
g diamagnetic
g paramagnetic
p g
dipole moment
λabs 344 nm, 452 nm 357 nm, 475 nm
lifetime ∞ 0.22 μs
Eox + 1.09 V - 1.06 V
Ered - 1.30 V + 0.85 V
pKaI
p - 0.3 - 8.3
pKaII + 0.12 - 5.7
 200 nm
50,000 cm-1

PH
143 kcal/einstein

HOTOC
CHEMIISTRY
λ 800 nm
12,500 cm-1
36 kcal/einstein

Energies of some chemical bonds

O-O 35 Kcal/mol
C-C 80 Kcal/mol
C-H 100 Kcal/mol
ν, E O-H 105 Kcal/mol
 k (s-1) uncertainty principle
hν
A *A Δτ ~ 10-15 s ΔE ≥ 15 kcal/mol
τ = 1/k

k (s-1) t (s)
1015 10-15 femto, fs electronic motions
1012 10-12 pico, ps
vibrational motions
events of 109 10-9 nano, ns
photochemical
106 10-6 micro, ms rotational,
interest
translational
103 10-3 milli, ms
motions
100 100 -, s
10-3 103 kilo Ks
kilo, “ordinary”
y chemistry
y
10-6 106 mega, Ms
macroscopic
10-9 109 giga, Gs lifetime of man
events
10-12 1012 tera, Ts age of the earth
10-15 1015 penta, Ps age of the universe
 B photoreaction

A + hν *A A + hν ’ luminescence
(radiative deactivation)

φ = quantum yield A + heat degradation to heat

(
(non radiative
di ti deactivation)
d ti ti )

number of photons hν’ emitted

φ hν ’ =
number of photons hν absorbed

number of molecules of B formed

φB =
number of photons hν absorbed

b off molecules
number l l off A which
hi h disappears
di
φ-A =
number of photons hν absorbed
Molecules present different electronic excited states
A + hν’’
kr2

kisc kp2
A + hν **A
A *A
A C
kr1 knr1
knr2
kp11 A + heat
h t
A + hν ’ A + heat
B
E
**A kp1
kisc B
*A kp2
knr1 C
hν
kr1 kr2
knr2
radiative decay
A
non-radiative decay
simplified Jablonski diagram
 Each elementary step is characterized by its
- rate constant, ki
- efficiency ηi = ki/Σki

Each excited state is characterized by its

- lifetime
lif ti τ = 1/Σk
1/ ki

Each process, i.e. sequence of elementary steps, is characterized by its

number of molecules that undergo the process
- quantum yield, φ =
number of photons absorbed

Relationships between k, η, τ, φ
A + hν’’
ηi = ki τ φ = Πηi or φ = ΣΠηi kr2

kisc kp2
A + hν **A *A C
ηr1 = kr1/(kr1+knr1+kp1+kisc)
τ**A = 1 /(kr1+knr1+kp1+kisc) kr1 knr1
knr2
kp1 A + heat
ηr1 = kr1×τ**A A + hν ’ A+h
heatt
B φhν’’ = ηisc ηr2
φC = ηisc ηp2 φ-A = ηp1+ηisc ηp2 φhν’ = ηr1