!
ðMÞ
Cl 2 B
3 P 0
þ
u
À Á ; v B
À
Á ! Cl 2 X
1 R 0
þ
g
; v X
þ hv
ð7:2:42bÞ
(Figure 7.3) (see [22] and references) on helium pressure (Fig. 7.4), which is a
consequence of the factors listed above: the Cl 2 ðA
0
Þ
3 P 2 u
ð Þ, A
3 P 1 u
ð Þ, B
03 P 0
À
u
À Á
correlating with the Cl + Cl dissociation limit collisionally mix with each other as
well as with the Cl 2 ðB
3 P 0
þ
u
À Á
state correlating with the Cl + Cl* dissociation
limit.
The mechanism of reactions (7.2.42) has been described as follows:
Cl þ Cl $ Cl 2 A
0
; v
max
A 0 ; A; v
max
v A
; B
0
; v
max
B 0
ðÀ7:2:43Þ
Cl 2 A
0
; v
max
A 0 ; A; v
max
v A
; B
0
; v
max
B 0
!
M Cl 2 A
0
; v A 0 ; A; v A ; B
0
; v B 0
ð
Þ
ð 7:2:44Þ
Cl 2 A
0
; v A 0 ; A; v A ; B
0
; v B 0
ð
Þ $
M Cl 2 B; v B
ð
Þ
ð7:2:45Þ
Cl 2 A; v A ; B; v B
ð
Þ !Cl 2 X; v X
ð
Þþhv
ð7:2:46aÞ
Cl 2 A
0
; v A 0 ; A; v A ; B
0
; v B 0 ; B; v B
ð
Þ ! Cl 2 X; v X
ð
Þþhv
ð7:2:46bÞ
Cl 2 A
0
; v A 0 ; A; v A ; B
0
; v B 0 ; B; v B
ð
Þ !
Cl
products
ð7:2:47Þ
Cl 2 A
0
; v A 0 ; A; v A ; B
0
; v B 0 ; B; v B
ð
Þ !
Cl 2
products !
ð 7:2:48Þ
Fig. 7.3 The Cl 2 potential energy RKR (—) and Morse (—) curves for bound states correlating
with the Cl(
2
P 3/2 ) + Cl(
2
P 3/2 ) and Cl(
2
P 3/2 ) + Cl(
2
P 1/2 ) dissociation limits. Cl = Cl(
2
P 3/2 ),
Cl
* = Cl(
2
P 1/2 ). The position of the Cl 2 (B,v B ) vibrational levels is marked as lines
280
7 Chemiluminescence