Ground state
reactants
Excited state
reactants
Orbital occupancy
Carbonyl photochemistry
Vibrational structure
Frank Condon
Anthracene
ST gaps
Intersystem crossing
Reaction
Intermediates
Ground state
products
Some kinetics
Delayed fluorescence
Excimers and exciplexes
Energy gap law
Fluorescence yields
Correlation diagrams
Energy transfer
Sensitization and quenching
3.1
Kinetic terms
Decay of reaction intermediates with lifetimes
of 25 ns (A) and 100 ns (B).
100
[Conc]
80
[Conc] =
2.718
60
concentration
B
A
40
20
0
0
20
-1
= k
40
60
80
Time, ns
1
2
100
ln 2
k
120
0.69
k
3.2
Endothermic but
accessible at room T
S1
ISC
T1
S0
3.3
Triplet
61
Triplet
61
91
Triplet-triplet encounters
Spin considerations:
1/9 singlets
3/9 triplets
5/9 quintets
3.4
Singlet
States
Excited state
reactants
Reaction
Intermediates
Ground state
products
Triplet
States
Fluorescence emission
The triplet state behaves as
a parking lot for the singlet
state, which emits with a lifetime
directly related to the triplet
lifetime in the system.
3.5
E and P mechanisms
Triplet State
P type
delayed fluorescence
E type
delayed fluorescence
no thermal activation
thermally activated
spin allowed
mobility required
3.6
Stabilization by association
3.7
Stabilization by association
Ground state
Excited state
no stabilization
electron stabilization
3.8
3.9
Excited state
concentration
3.10
EXCIMER
EXCIPLEX
3.11
Singlet
States
ic
= 10
13
- E
(sec
-1
ISC
Triplet
States
exp(- E)
Ground
Singlet
State
3.13
Quantum yields
3.14
CH3
CH3
0.2
,* , rigid
0.7
,* , rigid
0.05
,* , flexible
0.001
< 0.0001
n,* , flexible,very
small ST gap
3.15
O* + HX
CH3
OH
+ X
CH3
3.16
-1 -1
(in units of 10 M s )
Benzophenone
triplet
(CH ) CO
Cyclohexane
0.45
1.6
Methanol
0.21
0.29
Benzhydrol
7.5
7.2
Triethylsilane
9.6
5.7
CH3
CH3
O* + HX
CH3
CH3
3 3
OH
+ X
3.17
Energy transfer
M*
Q*
3.18
D*
h + A
D + h
A*
3.19
e2
R
donor
acceptor
3.20
donor
acceptor
8RT 2 x 10 5 T
k diff = 2000
10
-1
isopentane
4.6
benzene
1.6
water
1.1
-1
3.22
hn
D* + A
D*
D + A*
D is a sensitizer for A
A is a quencher for D*
3.23
S1
91
N
1
S1
85
N* + K
1
T1
T1
78
60
CH 3
O
H 3C
CH 3
K*
K* + N
N*
N +
3
K*
K*
K +
N*
3.24