Chapter 7
Chemiluminescence
Abstract Chemiluminescence reactions are discussed in this chapter. In the
beginning, definitions of various types of reactions and their rate constants are
introduced. The primary attention is paid to considering various types of recombination accompanied by radiation, namely, inverse dissociation, inverse electronic
predissociation, and termolecular recombination accompanied by radiation. Some
exciting features of these processes are discussed.
7.1 Types of Chemiluminescent Processes. Rate Constants.
Definitions
1. Chemiluminescent reactions are processes of species collisions, accompanied by
a change in their chemical composition and photon emission, and processes of
recombination of colliding species into a short-lived complex (quasi-molecule),
part or all of the excitation energy of which is disappeared by photon radiation.
Without the second part of the definition, species collision processes lead to the
formation of electronically excited complexes, including bound ones, and the
radiative transition to the repulsive (therefore, there is no change in chemical
composition) state of the complex cannot be considered as chemiluminescence.
Recombination of the Xe
1 S
ð ÞþO
1 D
ð Þ (see Fig. 5.21) is an example of such
processes.
Xe
1 S
À Á þ O
1 D
À Á $ XeO a
1 R
þ
; b
1 P
À
Á !
#
XeO X
3 P
ð Þþ hv
Xeð 1 SÞ þ O 3 P
ð Þ
ð7:1:1Þ
Under the change in chemical composition in this definition, we should also
understand the process of exchange of two identical species, which can be registered in the form of isotopic exchange.
© Springer Nature Switzerland AG 2021
A. Pravilov, Gas-Phase Photoprocesses, Springer Series in Chemical Physics 123,
https://doi.org/10.1007/978-3-030-65570-9_7
265
Chemiluminescence
Abstract Chemiluminescence reactions are discussed in this chapter. In the
beginning, definitions of various types of reactions and their rate constants are
introduced. The primary attention is paid to considering various types of recombination accompanied by radiation, namely, inverse dissociation, inverse electronic
predissociation, and termolecular recombination accompanied by radiation. Some
exciting features of these processes are discussed.
7.1 Types of Chemiluminescent Processes. Rate Constants.
Definitions
1. Chemiluminescent reactions are processes of species collisions, accompanied by
a change in their chemical composition and photon emission, and processes of
recombination of colliding species into a short-lived complex (quasi-molecule),
part or all of the excitation energy of which is disappeared by photon radiation.
Without the second part of the definition, species collision processes lead to the
formation of electronically excited complexes, including bound ones, and the
radiative transition to the repulsive (therefore, there is no change in chemical
composition) state of the complex cannot be considered as chemiluminescence.
Recombination of the Xe
1 S
ð ÞþO
1 D
ð Þ (see Fig. 5.21) is an example of such
processes.
Xe
1 S
À Á þ O
1 D
À Á $ XeO a
1 R
þ
; b
1 P
À
Á !
#
XeO X
3 P
ð Þþ hv
Xeð 1 SÞ þ O 3 P
ð Þ
ð7:1:1Þ
Under the change in chemical composition in this definition, we should also
understand the process of exchange of two identical species, which can be registered in the form of isotopic exchange.
© Springer Nature Switzerland AG 2021
A. Pravilov, Gas-Phase Photoprocesses, Springer Series in Chemical Physics 123,
https://doi.org/10.1007/978-3-030-65570-9_7
265