Physical Chemistry 3: — Chemical Kinetics — - Christian-Albrechts ...

12.4 Radiationless processes in photoexcited molecules 249
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Figure 12.4: Avoided crossing of two potential curves of a diatomic molecule.
Avoided Crossing of Two Potentials of a Diatomic Molecule
Adiabatic potential curves: V1
( R) W( R)
H
W( R) V2( R)
V
V1
( R) W( R)
R
Eigenvalues
WR ( ) V2( R)
Physical Chemistry III: Chemical Kinetics • © F. Temps, IPC Kiel 255
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Figure 12.5: Avoided crossing of two potential curves of a diatomic molecule. At the
avoided crossing the characters of the adiabatic potential curves switch.
Avoided Crossing of Two Potentials of a Diatomic Molecule
V E W V V V V
1 2 1 2 1 2
0 E
W
with: ;
W V2
E
2 2
2
V ( R) ( R) ( R) W( R)
"Avoided Crossing" with
Splitting of 2 |W( R x ) |
Physical Chemistry III: Chemical Kinetics • © F. Temps, IPC Kiel 256