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

7.2 Applications of transition state theory 156
7.2.2 Example 1: Reactions of two atoms A + B → A···B ‡ → AB
This example is somewhat artifical unless there is some mechanism to remove the bond
energy (for example, in associative ionization, A + B → A···B ‡ → AB + + − ).
‡ µ
exp − ∆
0
Ã
! Ã !
= ‡
‡
( )( ) 1
= µ
2 ( + ) 2
2 2
µ
× exp − ∆
0
= µ
2
+
2
µ
× exp − ∆
0
( )=
µ
exp − ∆
0
2
2
32 µ 8 2 ‡
2
32
Ã
!
8 2 ( + ) 2
2 +
y
µ 12 µ
8
( )=
( + ) 2 exp − ∆
0
This result is identical to that obtained by the LC model in collision theory!
(7.42)
(7.43)
(7.44)
(7.45)
(7.46)