Elementary reaction

• The elementary reaction rate is determined by integrating the reaction

cross section or probability over the relevant distribution function.
• This integration provides insights into the energy or excitation state of
the reactants.
• Micro-kinetic characteristics of individual reactive collisions, such as
reaction cross sections and elementary reaction probabilities, influence
the rate.
• Factors such as the electron energy distribution function (EEDF) and
the population function of excited molecular states also impact the
elementary reaction rate.
1
Electron energy distribution function

2
3
4
• In physical chemistry, the Arrhenius equation is a formula for the
temperature dependence of reaction rates 5, for the temperature
dependence of equilibrium constants suggests such a formula for the rates
of both forward and reverse reactions. This equation has a vast and
important application in determining the rate of chemical reactions and for
calculation of energy of activation. Arrhenius provided a physical
justification and interpretation for the formula.[1][2][3][4] Currently, it is best
seen as an empirical relationship.[5]: 188 It can be used to model the
temperature variation of diffusion coefficients, population of crystal
vacancies, creep rates, and many other thermally-induced
processes/reactions. The Eyring equation, developed in 1935, also
expresses the relationship between rate and energy.
5
6
 • Usually, the number densities of electrons and
Elementary Charged positive ions are equal or close in quasineutral
plasmas, but in “electronegative” gases (like O2,

Particles in Plasma Cl2, SF6, UF6, TiCl4,etc.) with high electron

affinity, negative ions are also effectively
formed.

7
• Different kind of plasmas in astrophysics, solar physics and solid state
physics, nuclear fusion, and for technical applications in a plot of
electron temperature vs. electron density. The green line denotes the
limitation of nonrelativistic plasmas, degenerate and non-ideal
plasmas are positioned right from the blue and red lines, respectively.

8
Electrons and energy transfer
• Electrons are first in getting energy from electric fields, because of
their low mass and high mobility.
• Electrons then transmit the energy to all other plasma components,
providing energy for ionization, excitation, dissociation, and other
plasma-chemical processes.
• The rates of such processes depend on how many electrons have
enough energy to do the job.

9
Ionisation
• The first elementary plasma-chemical processes to be considered is :
Ionisation, which means conversion of neutral atoms or molecules
into electrons and positive ions.

10
Ionisation process
• In hot thermonuclear plasmas, the ions are multi-charged, but in
relatively cold plasmas of technological interest their charge is usually
equal to +1e(1.6 · 10−19 C).
•

11
Ionisation process
• Electron attachment leads to formation of negative ions with charge
−1e(1.6 · 10−19 C).

• Ions are heavy particles, they cannot receive high energy directly from
electric fields, but their energy balance is due to collisional processes.

12
Elastic and Inelastic Collisions
• The elastic collisions are those in which the internal energies of
colliding particles do not change; therefore, total kinetic energy is
conserved as well.

13
• The elastic processes result only in geometric scattering and
redistribution of kinetic energy. All other collisions, like ionization, for
example, are inelastic.
• Most inelastic collisions, like ionization, result in energy transfer from
the kinetic energy of colliding partners into internal energy.
Sometimes, however, the internal energy of excited atoms or
molecules can be transferred back into kinetic energy (in particular,
into kinetic energy of plasma electrons). These elementary processes
are usually referred to as superelastic collision

14
Parameters
• The elementary processes can be described in terms of six major
collision parameters:
1. Cross section,
2. Probability ,
3. mean free path,
4. interaction frequency,
5. reaction rate ,
6. reaction rate coefficient.

15
Cross section
An imaginary circle of area σ, moving together with one of the collision
partners. If the centre of the other collision partner crosses the circle, then
the elementary reaction takes place.
Collisional cross section for two hard elastic spheres with radii r1 and r2

16
17
18
19
20
Cross section
• Interaction radius and cross section can surpass geometric sizes due to long-distance forces
between electric charges and dipoles.
• In cases where only a few out of many collisions lead to a chemical reaction, the cross section
is considered to be less than geometric.
•
When it is mentioned that the cross section is considered to be "less than geometric," it means
that the effective area involved in the interaction or collision is smaller than what would be
expected based solely on the geometric dimensions of the particles or objects involved.
• In the context of elementary plasma-chemical reactions, the geometric cross section would be
the cross-sectional area based on the physical size or dimensions of the particles. If the
effective cross section is less than geometric, it implies that factors such as the nature of the
forces, orientation, or other influences result in a reduced probability or area of interaction
compared to what would be anticipated purely based on the geometric characteristics of the
particles involved in the collision.

21
Probability
• The ratio of the inelastic
collision cross section to
the corresponding cross
section of elastic
collision in the same
condition sometimes is
called the dimensionless
probability of the
elementary process.

22
Mean free path
• λ It is the average of molecular free path length between consecutives
collisions, a straight path with unchanging velocity since the molecules
exert no force on one another except when they collide.

• λ of one collision A + B with can be calculated as:

λ = 1/nBσ
nB is the number density (concentration) of the particles B

23
Mean free path
• The mean free path λ of one collision partner A with respect to the
elementary process A + B with another collision partner, B, can be
calculated as:
λ = 1/nBσ
nB is the number density (concentration) of the particles B.

24
Derivation of the mean free path

25
Interaction frequency
• The interaction frequency ν of one collision partner A with B is the
ratio of their relative velocity v to the mean free path λ:

• This relation should be averaged, taking into account the velocity

distribution function f (v) and the dependence of cross section σ on the
collision partners’ velocity:

26
27
Reaction rate

28
Reaction rate
• For bimolecular processes A + B, the reaction rate can be calculated by
multiplication of the interaction frequency of partner A with partner B,
νA, and by the number of particles A in the unit volume (which is their
number density, nA):

wA+B = νAnA = σvnAnB.

29
Reaction rate coefficient
The factor σv is the so-called reaction rate coefficient, which can be
calculated for bimolecular reactions as
In contrast to the reaction cross section σ, which is a function of the
partners’ energy, the reaction rate coefficient k is an integral factor,
which includes information on the energy distribution functions and
depends on temperatures or mean energies of the collision partners.

30
Reaction rate coefficient

31
32
33
34
35
36
37
38
39
40
41
42
Classification of Ionization Processes
• Direct ionization by electron impact
• Stepwise ionization by electron impact
• Ionization by collision of heavy particles
• Photo-ionization
• Surface ionization (electron emission)

43
Direct ionization by electron impact
• It is an ionization of neutral and previously unexcited atoms, radicals,
or molecules by an electron whose energy is high enough to provide
the ionization act in one collision.
• Ionization occurs when the energy ε transferred to the valence
electron exceeds the ionization potential.
• These processes are the most important in cold or non-thermal
discharges, where electric fields and therefore electron energies are
quite high, but where the excitation level of neutral species is
relatively moderate.

44
Direct Ionization by Electron Impact:
Thomson Formula

45
46
Direct Ionization by Electron Impact:
Frank-Condon Principle and Dissociative Ionization

47
• The ground and excited electronic states are represented by so-called potential energy (PE) curves.
• Each electronic state has its associated PE curve (so called because it is regarded as an
effective potential that governs the motion of the nuclei), which varies as a function of the internuclear
separation, R.
• The equilibrium bond length, Re, of the ground state molecule is the internuclear separation at which
the potential curve for this state has a minimum.
• In Fig. 3a, the potential curve for the excited state has its minimum at R = ∞ and is purely repulsive.
• Electronic excitations are thus represented as vertical transitions between such PE curves. The nuclei
adjust to their new electronic environment after promotion to the excited state potential, in this case by
separating into two free atoms on a timescale of the order of one half of a vibrational period ( ∼10 −13 to
10−14 sec).
• Fragmentations of this kind are termed direct dissociations. Transitions to such short-lived, purely
dissociative excited states reveal themselves as broad, continuous features in absorption spectroscopy.
HF and HCl are examples of molecules that fragment in this way following excitation in the VUV
spectral region.
48
• Molecular dissociations are normally considered in a number of subcategories. Figure 3 illustrates two generic
types of fragmentation mechanism for diatomic molecules. In Fig. 3a, photoexcitation promotes a molecule from
a bound ground state to an excited electronic state that has no net bonding and thus dissociates directly into its
constituent atoms. The ground and excited electronic states are represented by so-called potential energy (PE)
curves. These are theoretical constructs obtained by invoking the Born-Oppenheimer approximation and solving
the Schrödinger equation for the two nuclei and the ensemble of electrons that, together, make up the molecule.
In this picture, each electronic state has its associated PE curve (so called because it is regarded as an
effective potential that governs the motion of the nuclei), which varies as a function of the internuclear
separation, R. The equilibrium bond length, Re, of the ground state molecule is the internuclear separation at
which the potential curve for this state has a minimum. In Fig. 3a, the potential curve for the excited state has its
minimum at R = ∞ and is purely repulsive. The act of photon absorption occurs so rapidly that the molecule has
no opportunity to adjust its bond length during the transition. Electronic excitations are thus represented as
vertical transitions between such PE curves. The nuclei adjust to their new electronic
environment after promotion to the excited state potential, in this case by separating into two free atoms on a
timescale of the order of one half of a vibrational period (∼10−13 to 10−14 sec). Fragmentations of this kind are
termed direct dissociations. Transitions to such short-lived, purely dissociative excited states reveal themselves
as broad, continuous features in absorption spectroscopy. HF and HCl are examples of molecules that fragment
in this way following excitation in the VUV spectral region.
49
• Such behavior should be contrasted with that which would occur in the case of a
molecule with PE curves arranged such as in Fig. 3b. The key point to note in this case
is that there is a region of configuration space (here corresponding to an internuclear
separation larger than the ground state equilibrium bond length) at which the PE of a
bound excited state matches that of a second, dissociative electronic state. Initial
photoexcitation from the ground state, at or above this energy, will result in population
of the “bound” vibrational level, but as the bond extends the excited electronic
configuration will evolve, acquiring more of the character of the dissociative state. Each
time the nuclei sample the extended geometry they can choose whether to follow the
bound or repulsive potential; those that follow the former execute another
molecular vibration, but those taking the latter route continue to separate from one
another, forming atomic fragments. Such dissociation is termed predissociation, because
the dissociation occurs at an energy below that of the natural dissociation limit of the
initially populated bound state.
50
• Clearly, predissociation rates can span many orders of magnitude, depending upon the efficiency
of the coupling between the bound and repulsive state potentials. The energy-time form of the
Uncertainty Principle
• (2)δE≈ħ�
• requires that the energy of an ensemble of molecules in an excited state with average lifetime τ
will be blurred to an extent of order δE. Transitions to levels that predissociate very rapidly (i.e.,
have small τ) show substantial “lifetime broadening”; e.g., an excited state with τ = 10−13 sec will
exhibit associated lifetime broadened linewidths of ∼53 cm−1 which may prove hard to
distinguish from a direct dissociation simply by inspection of the (apparently continuous)
absorption spectrum. In contrast, transitions to only weakly predissociated levels can appear as
resolved rovibrational structures in absorption spectroscopy and, in extreme cases, the weakly
predissociated excited states may exhibit measurable fluorescence quantum yields. The VUV
absorption spectra of virtually all diatomic molecules show some fine structure attributable to
predissociated excited states when viewed at sufficiently high spectral resolution.

51
• The electronic state density changes little upon progressing from diatomic to
polyatomic molecules, but the complexity of the nuclear motions, particularly the
number of vibrational degrees of freedom and thus the vibrational state density,
increases dramatically. Inevitably, this leads to further spectral congestion, but,
more importantly from the photochemical viewpoint, also means that examples of
simple direct dissociations (as described above for a diatomic molecule) are rare in
the case of electronically excited polyatomic molecules. Much more commonly,
the excited molecule will fragment after intramolecular vibrational redistribution
(IVR) either within the initially prepared excited state (often
termed vibrational predissociation) or after radiationless transfer (e.g., internal
conversion) to an unbound potential energy surface (PES). This latter mechanism
is the polyatomic analogue of the electronic predissociation process described
above for the case of a diatomic fragmentation.
52
• Dissociation - an overview | ScienceDirect Topics
• https://www.sciencedirect.com/topics/earth-and-planetary-
sciences/dissociation

53
Direct Ionization by Electron Impact:
Frank-Condon Principle and Dissociative Ionization
• Non-dissociative ionization of molecules by direct electron impact can
be presented for the case of diatomic molecules AB as :

e + AB → AB+ e + e.

• This process takes place when the electron energy does not greatly
exceed the ionization potential.

54
• Fig. 2–2. The fastest internal motion of atoms inside molecules is
molecular vibration. But even molecular vibrations have typical time
periods of 10−14–10−13 s, which are much longer than the
interaction times between plasma electrons and the molecules: a0/ve
∼ 10−16–10−15 s (where a0 is the atomic unit of length and ve is the
mean electron velocity).
• It means that all kinds of electronic excitation processes under
consideration, induced by electron impact (including the molecular
ionization; see Fig. 2–1), are much faster than all other atomic
motions inside

55
• According to the Frank-Condon principle, the processes of collisional
excitation and ionization of molecules are presented in Fig. 2–2 by
vertical lines.
• The non-dissociative ionization process (2–19) usually results in the
formation of a vibrationally excited ion (AB+) ∗ and requires a little
more energy than corresponding atomic ionization.

56
Direct Ionization by Electron Impact:
Dissociative ionisation
• When the electron energy is relatively high and substantially exceeds
the ionization potential, the dissociative ionization process can take
place:
e + AB → A + B+ e + e.

• This ionization process corresponds to electronic excitation into a

repulsive state of the ion, (AB+) ∗, followed by a decay of this
molecular ion

57
• It is also illustrated by a vertical line in Fig. 2–2. One can see from Fig.
2–2 that the energy threshold for the dissociative ionization is
essentially greater than that for the non-dissociative one.

58
Direct Ionization by Electron Impact:
Frank-Condon Principle and Dissociative Ionization
• Data on the electron impact direct
ionization for different molecular gases
(CO2, H2, N2, etc.) are presented in Fig. 2–3
as a function of reduced electric field E/n0,
which is the ratio of the electric field over
the neutral gas concentration

• Rate coefficients of ionization by direct

electron impact in molecular gases (CO2,
H2, N2–H2, CO) as a function of reduced
electric field.
59
• This ionization process corresponds to electronic excitation into a
repulsive state of the ion, (AB+) ∗, followed by a decay of this
molecular ion. It is also illustrated by a vertical line in Fig. 2–2. One
can see from Fig. 2–2 that the energy threshold for the dissociative
ionization is essentially greater than that for the non-dissociative one.
Data on the electron impact direct ionization for different molecular
gases (CO2, H2, N2, etc.) are presented in Fig. 2–3 as a function of
reduced electric field E/n0, which is the ratio of the electric field over
the neutral gas concentration

60
Stepwise ionization by electron impact
• Faster than direct ionization, stepwise ionisation is ionization of
preliminary excited neutral species. These processes are important
mostly in thermal or energy-intense discharges, when the ionization
degree ne/n0 as well as the concentration of highly excited neutral
species is quite high.
• For quasi-equilibrium or thermal plasmas
e + A → A+ + e + e
A+ + e + e → A∗ + e → A + e
e + A → A+ + e + e

61
Stepwise ionization by electron impact
• When the plasma density and, therefore, the concentration of excited
neutrals are high enough, the energy (I) necessary for ionization can
be provided in two different ways :
• First: like in the case of direct ionization, it could be provided by
the energy of plasma electrons.
• Second: the high energy of preliminary electronic excitation of
neutrals can be converted in the ionization act, which is called
stepwise ionization
• the stepwise ionization rate coefficient can be expressed:

62
• At first, electron–neutral collisions prepare highly excited species, and then a final
collision with a relatively low-energy electron provides the actual ionization event.
• In thermodynamic equilibrium, the ionization process
• e + A → A+ + e + e
• is inverse to the three-body recombination
• A+ + e + e → A∗ + e → A + e,
• which proceeds through a set of excited states. According to the principle of detailed
equilibrium, the ionization process
• e + A → A+ + e + e
• should go through the set of electronically excited states as well, which means the
ionization should be a stepwise process. However, this conclusion can only hold true for
quasi-equilibrium or thermal plasmas.
63
Ionization by collision of heavy particles
• It takes place during ion–molecule or ion–atom collisions, as well as in
collisions of electronically or vibrationally excited species, when the
total energy of the collision partners exceeds the ionization potential.
• The chemical energy of colliding neutral species can also contribute
to ionization in the so-called associative ionization processes.
• The electron energy in electron beams applied today usually varies
from 50 KeV to 1–2 MeV. Typical energy losses of the beams in
atmospheric-pressure air are about 1 MeV per 1m(≈ 1 keV/mm).
• Generation of large plasma volumes for this reason requires high
electron energies in the beams.
64
Ionization by collision of heavy particles:
Bethe-Bloch Formula
• Electron energy losses per unit length, d E/dx, can be evaluated in the
non-relativistic case by the Bethe-Bloch formula: −d E dx = 2π Ze4
(4πε0)2mv2 n0 ln 2m Ev2 I 2

• effective ionization rate coefficient keff i for relativistic electrons:

65
Photo-ionization
• It takes place in collisions of neutrals with photons, which result in the
formation of an electron–ion pair. Photo-ionization is mostly
important in thermal plasmas and in some mechanisms of
propagation of non-thermal discharges.
• Photo-ionization of a neutral particle A with ionization potential I (in
electron volts) by a photon hω with wavelength λ can be illustrated
as:

66
• To provide the ionization, the photon wavelength should be usually
less than 1000 Å, which is ultraviolet radiation. The photo-ionization
cross section increases sharply from zero at the threshold energy (2–
32) to quite high values – up to the geometrical cross section. The
photo-ionization cross sections for some atoms and molecules are
presented in Table 2–1. The cross sections presented in Table 2–1 are
quite high. The contribution of the photoionization process is usually
not very significant because of low concentrations of highenergy
photons in most discharge systems. However, sometimes photo-
ionization plays

67
Ionization by collision of heavy particles:
Adiabatic Principle and Massey Parameter

68
Surface ionization (electron emission)
• provided by electron, ion, and photon collisions with different
surfaces or simply by surface heating. This ionization mechanism is
quite different from the first four

69
Penning Ionization Effect and Associative
Ionization
• If the electronic excitation energy of a metastable atom A∗ exceeds
the ionization potential of another atom B, their collision can lead to
an act of ionization, the so-called Penning ionization.

70
Penning Ionization Effect and Associative
Ionization
• The Penning ionization usually proceeds through the intermediate
formation of an unstable excited quasi molecule in the state of auto-
ionization; cross sections of the process can be very high.

71
72
73
Penning Ionization Effect and Associative
Ionization
• The Penning ionization usually proceeds through the intermediate
formation of an unstable excited quasi molecule in the state of auto-
ionization; cross sections of the process can be very high.
• Cross sections for the Penning ionization of N2, CO2, Xe, and Ar by
metastable helium atoms He(23S) with an excitation energy of 19.8 eV
reach gas-kinetic values of about 10−15 cm2.
• Similar cross sections can be attained in collisions of metastable neon
atoms (excitation energy 16.6 eV) with argon atoms (ionization
potential 15.8 eV).

74
75
Associative ionization
• If the total electronic excitation energy of colliding particles is not
sufficient, ionization is still possible when heavy species stick to each
other, forming a molecular ion. Such a process is called the
associative ionization; for example,

76
Associative Ionisatin
A∗ + B → AB+ + e
• It takes place effectively when there is a crossing of the electronic
energy term of the colliding particles with an electronic energy term
of the molecular ion AB+ and, as a result, the process is nonadiabatic.

• Such a situation takes place only for a limited number of excited

species.

77
• Ionization during collision of vibrationally excited molecules can be very
important in non-equilibrium systems. Cross sections of such processes,
however, are very low because of the smallness of the Frank-Condon
factors. Consider the associative ionization (Rusanov & Fridman, 1984)

• The nitrogen molecules with 32 vibrational quanta each have enough

energy for the associative ionization, but the reaction rate of the process is
relatively low: 10−15exp(−12000 K/T), cm3/s. More information regarding
ionization in collisions of vibrationally excited molecules can be found in
Adamovich et al. (1993) and Plonjes et al. (2001)
78
• The total electronic excitation energy here (9.6 eV) is less than the
ionization potential of mercury atoms (10.4 eV) but higher than
ionization potential for a Hg− 2 molecule. This is actually the main
“trick” of the associative ionization.
• Cross sections of the associative ionization (similar to the Penning
ionization) can be quite high and close to the gas-kinetic value (about
10−15 cm2).

79
ELEMENTARY PLASMA-CHEMICAL
REACTIONS INVOLVING NEGATIVE
IONS

80
 Electron–Ion Recombination in Plasma
• It is an exothermic
process.

• The process has a specific

channel of accumulation
of the energy released
during the neutralization
of a positive ion and an
electron: dissociation of
molecules or to three-
body collisions or to
radiation.
81
82
83
84
Major groups of mechanisms of electron–ion
recombination.
Electron neutralisation in molecular gases/ions due to
Dissociative electron–ion recombination

Recombination energy in these processes goes into dissociation of the

intermediately formed molecule ion and to excitation of the dissociation
products.
The fastest electron neutralization mechanism in molecular gases, or in
the presence of molecular ions.
Formation of molecular ions in the ion conversion processes:
85
Major groups of mechanisms of electron–ion
recombination.
Electron-ion neutralisation in atomic gases in absence of ions is due to
Three-body electron–ion recombination

Energy excess in this case is going into the kinetic energy of a free
electron, which participates in the recombination act as “a third-body
partner.”
We must remark that heavy particles (ion and neutrals) are unable to
accumulate electron recombination energy fast enough in their kinetic
energy and, therefore, are ineffective as the third body partner.
86
Major groups of mechanisms of electron–ion
recombination.
Recombination energy can be converted into radiation in the process of
Radiative electron–ion recombination

The cross section of this process is relatively low and can compete with
the three-body recombination only when the plasma density is not
high.

87
Major groups of mechanisms of electron–ion
recombination.
Formation of molecular ions in the ion conversion processes:

If the pressure is high enough, the recombination of atomic ions like Xe+
proceeds faster, not by means of or radiative mechanisms but through the
preliminary formation of molecular ions, that is, through the so-called ion
conversion reactions such as:

Then the molecular ion can be quickly neutralized in the rapid process of
dissociative recombination.
88
89
Ion–Molecular Reactions
• Electron–electron, electron–ion, and ion–ion scattering processes are
the so-called Coulomb collisions.
• An important feature of Coulomb collisions is a strong dependence of
their cross sections on the kinetic energy of colliding particles
• If one collision partner is considered at rest. A scattering event takes
place if the Coulomb interaction energy (U ∼ q2/b, where b is the
impact parameter) is about the kinetic energy ε of a moving particle.
• Then, the impact parameter (b ∼ q2/ε) and the reaction cross
section σ can be estimated as πb2:

90
Ion–Molecular Reactions
• The ion–molecular processes start with scattering in a polarization
potential, leading to the so-called Langevin capture of a charged
particle and formation of an intermediate ion–molecular complex.
• If a neutral particle itself has no permanent dipole moment, the ion–
neutral charge-dipole interaction is due to dipole moment Pm,
induced in the neutral particle by the electric field E of an ion

91
• r is the distance between the interacting particles, and α is the
polarizability of a neutral atom or molecule, which is numerically
about the volume of the atom or molecule

92
Langevin scattering in polarization potential
at different impact parameters.
• When the impact parameter is
high then the orbit is hyperbolic,
but when it is low then the
scattering leads to the Langevin
polarization capture and the
formation of an Ion–molecular
complex.

93
• The capture occurs when the charge-dipole interaction pm E = α e 4πr
2 e 4πε0r 2 becomes the order of kinetic energy 1 2 Mv2

94
Ion–Atomic Charge Transfer Processes and
Resonant Charge Transfer
• The charge exchange processes correspond to an electron transfer
from a neutral particle to a positive ion or from negative ion to a
neutral particle.
• If the reaction has no defect of electronic energy, deltaE, it is called a
resonant charge transfer; otherwise it is referred to as being non-
resonant.
• The resonant charge transfer is non-adiabatic and is characterized by
a large cross section

95
charge exchange between a neutral particle B
and a positive ion A+
• Supposing particle B/B+ is at rest,

96
97
98
Non-Resonant Charge Transfer Processes and
Ion–Molecular Chemical Reactions
•;

99
• The O-to-N electron transfer is an example of non-resonant charge
exchange with a 1-eV energy defect.
• The ionization potential of oxygen (I = 13.6 eV) is lower than that of
nitrogen (I = 14.5 eV).
• which is why the electron transfer from oxygen to nitrogen is an
exothermic process and the separated N + O+ energy level is located
0.9 eV lower than that for O + N+.

100
• Illustrative potential curves are shown in Fig. 2–6. The ionization potential
of oxygen (I = 13.6 eV) is lower than that of nitrogen (I = 14.5 eV), which is
why the electron transfer from oxygen to nitrogen is an exothermic process
and the separated N + O+ energy level is located 0.9 eV lower than that for
O + N+. The reaction starts with N+approaching O by the attractive NO+
energy term. Then, this term crosses with the repulsive NO+ term and the
system undergoes a non-adiabatic transfer, which results in the formation
of O+ + N. The cross section of such exothermic charge exchange reactions
at low energies is the order of resonant cross sections with tunneling or
Langevin capture (2–56)–(2–60). The endothermic reactions for charge
exchange, like the reverse process N + O+ → N+ + O, are usually very slow
at low energies.
101
non-resonant charge exchange can be illustrated
by the acidic behavior of non-thermal air plasmas.
• Ionization of air in non-thermal discharges primarily leads to large
amounts of N+ 2 ions (with respect to other positive ions) because of
the high molar fraction of nitrogen in air.

• The low ionization potential and high dipole moment of water

molecules enable the following charge exchange:

102
H3O+ ions and OH radicals
• The whole ionization process in air, as a result, can be significantly
focused on the formation of water ions (H2O+) even though the
molar fraction of water is low.

• The generated water ions can then react with neutral water
molecules via the quite fast ion–molecular reaction:

103
• Production of H3O+ ions and OH radicals determines the acidic
behavior of an air plasma, which is in particular a fundamental basis
for plasma application for air purification from different pollutants.

104
chemical bonds for negative and positive Ions
• These elementary processes can be subdivided into many groups, in
particular the following:

• (A)B+ + C → A + (C)B+: reactions with an Ion transfer

• A(B+) + C → (B+) + AC: reactions with a neutral transfer
• (A)B+ + (C)D → (A)D + (C)B+: double exchange reactions
• (A)B+ + (C)D → AC+ + BD: reconstruction processes

105
Dissociative Electron Attachment to Molecules as a Major
Mechanism of Negative Ion Formation in Electronegative
Molecular Gases
• The dissociative attachment is effective when the products have
positive electron affinities:

• The mechanism of the process is similar to the dissociative

recombination and proceeds by intermediate formation of an auto-
ionization state (AB−) ∗.
• This excited state is unstable and decays, leading either to the reverse
reaction of auto-detachment (AB + e) or to the dissociation (A + B−).

106
Elementary process of dissociative
attachment in the case of low electron affinity
•;

107
• An electron is captured during the attachment and is not able to
provide the energy balance of the elementary process. Therefore, the
dissociative attachment is a resonant reaction requiring a quite
definite electron energy. Typical potential energy curves (2–67) are
presented in Fig. 2–7. The process starts with a vertical transition
from the AB ground state to a repulsive state of AB− following the
Frank-Condon principle (Section 2.1.6). During the repulsion, before
(AB−) ∗ reaches the intersection point of AB and AB− electronic
terms, the reverse auto-detachment reaction (AB + e) is very possible.
But after passing the intersection, the AB potential energy exceeds
that of AB− and further repulsion results in dissociation (A + B−).
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