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Si Thu Han
Date – 19.04.2020
Reference Book - Plasma Chemistry
Chapter 2 Elementary Plasma-Chemical Reactions
Page 12 ~ 20, A. 2.1.1 - 2.1.8
Contents
1. Elementary Charged Particles in Plasma
4. Elastic Scattering and Energy Transfer in Collisions of Charged Particles: Coulomb Collisions
6. Specific Features of Ionization of Molecules by Electron Impact: Frank-Condon Principle and Dissociative
Ionization
9. Conclusion
2.1.1 Mechanism of the plasma-chemical process.
• Electrons are first in getting energy from electric fields, because of their low mass
and high mobility
2.1.2. Elastic and Inelastic Collisions and Their Fundamental Parameters
The elastic collisions are those in which the internal energies of colliding particles do not change;
therefore, total kinetic energy is conserved.
Most in elastic collisions, like ionization, result in energy transfer from the kinetic energy of
colliding partners into internal energy
the internal energy of excited atoms or molecules can be transferred back into kinetic energy (in
particular, into kinetic energy of plasma electrons).
If two colliding particles can be considered hard elastic spheres of radii r1 and r2, their
collisional cross section is equal to π(r1 + r2)^2.
1. Direct ionization by electron impact is 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.
3. Ionization by collision of heavy particles takes place during ion–molecule or ion–atom collisions,
as well as in collision of electronically or vibrationally excited species, when the total energy of the
collision partners exceeds the ionization potential
4. Photo-ionization 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.
5. Surface ionization (electron emission) is 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 and will be considered separately later on in this chapter.
2.1.4. Elastic Scattering and Energy Transfer in Collisions of Charged Particles: Coulomb Collisions
Electron–electron, electron–ion, and ion–ion scattering processes are the so-called Coulomb
collisions.
Non-dissociative ionization of molecules by direct electron impact can be presented for the
case of diatomic molecules AB as
This process takes place when the electron energy does not greatly exceed the ionization potential.
As a result, all the atoms inside a molecule can be considered as being frozen during the process of electronic
transition,
This fact is known as the Frank-Condon principle.
When the electron energy is relatively high and substantially exceeds the ionization
potential, the dissociative ionization process can take place:
This ionization process corresponds to electronic excitation into a repulsive state of the
ion, (AB+)∗, followed by a decay of this molecular ion.
2.1.7. 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.
If the level of electronic excitation is high enough, stepwise ionization is much faster than direct ionization,
because the statistical weight of electronically excited neutrals is greater than that of free plasma electrons.
In this relation, Nn, gn, and εn are number densities, statistical weights, and energies of the electronically
excited atoms, radicals, or molecules, respectively; the index n is the principal quantum number.
From statistical thermodynamics, the statistical weight of an excited particle gn = 2gin2, where gi is the
statistical weight of an ion; N0 and g0 are concentration and statistical weights of ground-state particles,
respectively.
This means that excited particles with energy about εn = I − Te make the major contributions
This means that excited particles with energy about εn = I − Te
make the major contributions into sum . Taking into account that In ∼ 1/n^2, the
number of states with energy about εn = I − Te and ionization potential about In = Te
has
an order of n.
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
1 m (≈ 1 keV/mm).
• Inelastic: momentum is redistributed between particles but a fraction of the initial kinetic energy
is transferred to internal energy in one or more of the particles
• Superelastic: a third class also needs to be anticipated— here there is more kinetic energy
after the collision. Momentum is conserved and internal energy in the particles entering into a
collision is transferred into kinetic energy
• Electron and ion temperature can be measured by Langmuir Probe and by using these values,
plasma density can be calculated
• ionization rate coefficient value determine which gas species can be produced from the
specific type of plasma
Thank you for your attention!