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

5.4 Advanced collision theory 120
5.4.3 From differential cross sections σ (...) to reaction rate constants k (T )
I
Figure 5.16: The strategy.
I
1 → 2:Integration over angles:
0
( )=
Z 2 Z
0
0
( ) 0
( )sin (5.146)
I 2 → 3:Summation over all product quantum states α 0 :
( )= X 0
0
( ) (5.147)
I 3 → 4:Thermal averaging over initial quantum states α:
( )= X
× ( ) (5.148)
with the Boltzmann factor and the partition function
=
−
P
−
= −
(5.149)
= X
−
(5.150)
y
( )= X
( ) × −
(5.151)