! A i þ B i
ð4:1:3Þ
! AB
ÃÃ
þ hm
ð4:1:4Þ
$ AB
ÃÃ
ð4:1:5Þ
AB
Ã
ðv; JÞ !
M AB
ÃÃ
þ DE 1
ð4:1:6Þ
$
M AB
ÃÃ
ð4:1:7Þ
!
M AB
ÃÃ
þ DE 2 DE 2 \DE 1
ð
Þ
ð 4:1:8Þ
!
M AB
Ã
ðv À Dv; J À DJÞ þ DE
ð4:1:9Þ
!
M B i þ C i
ð4:1:10Þ
!
M products
ð4:1:11Þ
AB
Ã
ðv À Dv; J À DJÞ; AB
ÃÃ
!
M products
ð4:1:12Þ
B
Ã
k ! C j þ D j
ð4:1:13Þ
B
Ã
k !
M products
ð4:1:14Þ
B
Ã
k ! B
ÃÃ
k þ hm
ð4:1:15Þ
B
Ã
k !
M B
ÃÃ
k
ð4:1:16Þ
!
M B
Ã
k ðv À Dv; J À DJÞ
ð 4:1:17Þ
where AB*(v, J) are rovibronic states of the diatomic or polyatomic molecule
resulting after absorption by the molecule AB a photon of energy hm, AB** are all
other rovibronic states including the AB ground state, A i , B i are both their
fragments.
Photolysis processes are categorized as primary and secondary processes.
Primary photolysis process includes photon absorption by the molecule AB and
degradation of excited energy for the resultant rovibronic state AB*(v, J), both
80
4 Photolysis of Free Molecules