Secondary photolysis processes include the follows:
– collisional deactivation of AB*(v, J) into another electronic state, including the
ground state (electronic deactivation), it is the process proceeding with a large
AB*(v, J) energy loss DE 1 and excluding the possibility of returning to the AB*
(v, J) electronic state (4.1.6);
– collision-induced nonadiabatic transition, CINAT (see [6, 7] and references),
into another bound electronic state; this process proceeds with a low AB*(v,
J) energy loss and allows a reverse transfer (4.1.7);
– the process similar considered above proceeding with a loss of energy (DE 2 );
this process allows a reverse transfer only to lower rovibronic levels AB*(v-Dv,
J-DJ) (4.1.8);
– rotational, vibrational and rovibrational relaxation of AB*(v, J) within an
electronic state (4.1.9);
– collision-induced predissociation of AB*(v, J) into AB fragments, including
those of coinciding with AB photodecay products (in other words, with primary
products of photolysis or primary photoproducts) (4.1.10);
– reaction involving AB*(v, J) (4.1.11);
– decay processes of AB*(v-Dv, J-DJ) and AB** states (spontaneous and
collision-induced) including, dissociation, predissociation, and luminescence
(4.1.12);
– spontaneous decay of one of the photodecay products of AB*, B
Ã
k , into fragments, including those coincide with any of the photodecay products of AB
(4.1.13), they also include reaction with photodecay products of AB (4.1.10), B
Ã
k
collisional decay (4.1.14), luminescence of these products (4.1.15), electronic
deactivation (4.1.16), rotational, vibrational and rovibrational relaxation (4.1.17)
and so on.
W.A Noyes, P.A. Leighton [8] and, in the wake of them, H. Okabe [9], proposed
to also include as primary processes those occurring with the participation of AB*
(v, J) and M (4.1.6—4.1.12). They also proposed to assume by secondary processes
those in which photodecay products B i , C i participate (4.1.13–4.1.17).
Methodologically, in the case of the gas phase, such a definition is wrong as
follows. Such absolute quantum yields depend upon of kind and pressure of gases,
the ratio of the reactor surface area to its volume, and so on, i.e., they are not
molecular constants describing the molecule features.
The processes (4.1.6–4.1.12) are usual bi-, and termolecular processes with
excited species, which are not in thermodynamic equilibrium with the environment.
These processes should be described using rate constants depending on the AB*,
AB** states, rather than by the absolute quantum yields.
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4 Photolysis of Free Molecules
– collisional deactivation of AB*(v, J) into another electronic state, including the
ground state (electronic deactivation), it is the process proceeding with a large
AB*(v, J) energy loss DE 1 and excluding the possibility of returning to the AB*
(v, J) electronic state (4.1.6);
– collision-induced nonadiabatic transition, CINAT (see [6, 7] and references),
into another bound electronic state; this process proceeds with a low AB*(v,
J) energy loss and allows a reverse transfer (4.1.7);
– the process similar considered above proceeding with a loss of energy (DE 2 );
this process allows a reverse transfer only to lower rovibronic levels AB*(v-Dv,
J-DJ) (4.1.8);
– rotational, vibrational and rovibrational relaxation of AB*(v, J) within an
electronic state (4.1.9);
– collision-induced predissociation of AB*(v, J) into AB fragments, including
those of coinciding with AB photodecay products (in other words, with primary
products of photolysis or primary photoproducts) (4.1.10);
– reaction involving AB*(v, J) (4.1.11);
– decay processes of AB*(v-Dv, J-DJ) and AB** states (spontaneous and
collision-induced) including, dissociation, predissociation, and luminescence
(4.1.12);
– spontaneous decay of one of the photodecay products of AB*, B
Ã
k , into fragments, including those coincide with any of the photodecay products of AB
(4.1.13), they also include reaction with photodecay products of AB (4.1.10), B
Ã
k
collisional decay (4.1.14), luminescence of these products (4.1.15), electronic
deactivation (4.1.16), rotational, vibrational and rovibrational relaxation (4.1.17)
and so on.
W.A Noyes, P.A. Leighton [8] and, in the wake of them, H. Okabe [9], proposed
to also include as primary processes those occurring with the participation of AB*
(v, J) and M (4.1.6—4.1.12). They also proposed to assume by secondary processes
those in which photodecay products B i , C i participate (4.1.13–4.1.17).
Methodologically, in the case of the gas phase, such a definition is wrong as
follows. Such absolute quantum yields depend upon of kind and pressure of gases,
the ratio of the reactor surface area to its volume, and so on, i.e., they are not
molecular constants describing the molecule features.
The processes (4.1.6–4.1.12) are usual bi-, and termolecular processes with
excited species, which are not in thermodynamic equilibrium with the environment.
These processes should be described using rate constants depending on the AB*,
AB** states, rather than by the absolute quantum yields.
82
4 Photolysis of Free Molecules