Ionization

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Ionization or ionisation is the process by which an atom or a molecule acquires a

negative or positive charge by gaining or losing electrons, often in conjunction with other
chemical changes. The resulting electrically charged atom or molecule is called an ion.
Ionization can result from the loss of an electron after collisions with subatomic
particles, collisions with other atoms, molecules and ions, or through the interaction
with electromagnetic radiation. Heterolytic bond cleavage and heterolytic substitution
reactions can result in the formation of ion pairs. Ionization can occur through
radioactive decay by the internal conversion process, in which an excited nucleus
transfers its energy to one of the inner-shell electrons causing it to be ejected.

Contents

 1Uses
 2Production of ions
 3Ionization energy of atoms
 4Semi-classical description of ionization
 5Quantum mechanical description of ionization
o 5.1Tunnel ionization
 5.1.1Quasi-static tunnel ionization
 6Strong field approximation for the ionization rate
o 6.1Atomic stabilization/population trapping
o 6.2Non-sequential multiple ionization
o 6.3Multiphoton ionization of inner-valence electrons and fragmentation of polyatomic
molecules
 7Kramers-Henneberger frame and ionization phase effects
 8Dissociation – distinction
 9See also
 10References
 11External links

Uses[edit]
Everyday examples of gas ionization are such as within a fluorescent lamp or
other electrical discharge lamps. It is also used in radiation detectors such as
the Geiger-Müller counter or the ionization chamber. The ionization process is widely
used in a variety of equipment in fundamental science (e.g., mass spectrometry) and in
industry (e.g., radiation therapy).

Production of ions[edit]
Avalanche effect between two electrodes. The original ionization event liberates one electron, and each
subsequent collision liberates a further electron, so two electrons emerge from each collision: the ionizing
electron and the liberated electron.

Negatively charged ions are produced when a free electron collides with an atom and is
subsequently trapped inside the electric potential barrier, releasing any excess energy.
The process is known as electron capture ionization.
Positively charged ions are produced by transferring an amount of energy to a bound
electron in a collision with charged particles (e.g. ions, electrons or positrons) or with
photons. The threshold amount of the required energy is known as ionization potential.
The study of such collisions is of fundamental importance with regard to the few-body
problem, which is one of the major unsolved problems in physics. Kinematically
complete experiments,[1] i.e. experiments in which the complete momentum vector of all
collision fragments (the scattered projectile, the recoiling target-ion, and the ejected
electron) are determined, have contributed to major advances in the theoretical
understanding of the few-body problem in recent years.
Adiabatic ionization is a form of ionization in which an electron is removed from or
added to an atom or molecule in its lowest energy state to form an ion in its lowest
energy state.[2]
The Townsend discharge is a good example of the creation of positive ions and free
electrons due to ion impact. It is a cascade reaction involving electrons in a region with
a sufficiently high electric field in a gaseous medium that can be ionized, such as air.
Following an original ionization event, due to such as ionizing radiation, the
positive ion drifts towards the cathode, while the free electron drifts towards
the anode of the device. If the electric field is strong enough, the free electron gains
sufficient energy to liberate a further electron when it next collides with another
molecule. The two free electrons then travel towards the anode and gain sufficient
energy from the electric field to cause impact ionization when the next collisions occur;
and so on. This is effectively a chain reaction of electron generation, and is dependent
on the free electrons gaining sufficient energy between collisions to sustain the
avalanche.[3]
Ionization efficiency is the ratio of the number of ions formed to the number of electrons
or photons used.[4][5]

Ionization energy of atoms[edit]

Ionization energies of neutral elements.

The trend in the ionization energy of atoms is often used to demonstrate the periodic
behavior of atoms with respect to the atomic number, as summarized by ordering atoms
in Mendeleev's table. This is a valuable tool for establishing and understanding the
ordering of electrons in atomic orbitals without going into the details of wave functions or
the ionization process. An example is presented in the figure at right. The periodic
abrupt decrease in ionization potential after rare gas atoms, for instance, indicates the
emergence of a new shell in alkali metals. In addition, the local maximums in the
ionization energy plot, moving from left to right in a row, are indicative of s, p, d, and f
sub-shells.

Semi-classical description of ionization[edit]

Classical physics and the Bohr model of the atom can qualitatively
explain photoionization and collision-mediated ionization. In these cases, during the
ionization process, the energy of the electron exceeds the energy difference of the
potential barrier it is trying to pass. The semi-classical description, however, cannot
describe tunnel ionization since the process involves the passage of electron through a
classically forbidden potential barrier.

Quantum mechanical description of ionization[edit]

The interaction of atoms and molecules with sufficiently strong laser pulses leads to the
ionization to singly or multiply charged ions. The ionization rate, i.e. the ionization
probability in unit time, can only be calculated using quantum mechanics. In general, the
analytic solutions are not available, and the approximations required for manageable
numerical calculations do not provide accurate enough results. However, when the laser
intensity is sufficiently high, the detailed structure of the atom or molecule can be
ignored and analytic solution for the ionization rate is possible.
Tunnel ionization[edit]
Combined potential of an atom and a uniform laser field. At distances r < r0, the potential of the laser can be
neglected, while at distances with r > r0 the Coulomb potential is negligible compared to the potential of the
laser field. The electron emerges from under the barrier at r = Rc. Ei is the ionization potential of the atom.

Tunnel ionization is ionization due to quantum tunneling. In classical ionization, an

electron must have enough energy to make it over the potential barrier, but quantum
tunneling allows the electron simply to go through the potential barrier instead of going
all the way over it because of the wave nature of the electron. The probability of an
electron's tunneling through the barrier drops off exponentially with the width of the
potential barrier. Therefore, an electron with a higher energy can make it further up the
potential barrier, leaving a much thinner barrier to tunnel through and, thus, a greater
chance to do so. In practice, tunnel ionization is observable when the atom or molecule
is interacting with near-infrared strong laser pulses. This process can be understood as
a process by which a bounded electron, through the absorption of more than one
photon from the laser field, is ionized. This picture is generally known as multiphoton
ionization (MPI).
Keldysh[6] modeled the MPI process as a transition of the electron from the ground state
of the atom to the Volkov states.[7] In this model the perturbation of the ground state by
the laser field is neglected and the details of atomic structure in determining the
ionization probability are not taken into account. The major difficulty with Keldysh's
model was its neglect of the effects of Coulomb interaction on the final state of the
electron. As it is observed from figure, the Coulomb field is not very small in magnitude
compared to the potential of the laser at larger distances from the nucleus. This is in
contrast to the approximation made by neglecting the potential of the laser at regions
near the nucleus. Perelomov et al.[8][9] included the Coulomb interaction at larger
internuclear distances. Their model (which we call PPT model) was derived for short
range potential and includes the effect of the long range Coulomb interaction through
the first order correction in the quasi-classical action. Larochelle et al. [10] have compared
the theoretically predicted ion versus intensity curves of rare gas atoms interacting with
a Ti:Sapphire laser with experimental measurement. They have shown that the total
ionization rate predicted by the PPT model fit very well the experimental ion yields for all
rare gases in the intermediate regime of Keldysh parameter.
The rate of MPI on atom with an ionization potential  in a linearly polarized laser with
frequency  is given by
where
  is the Keldysh's adiabaticity parameter,
 ,
  is the peak electric field of laser and
 .
The coefficients ,  and  are given by
The coefficient  is given by
where
Quasi-static tunnel ionization[edit]
The quasi-static tunnelling (QST) is the ionization whose rate can be
satisfactorily predicted by the ADK model,[11] i.e. the limit of the PPT model
when  approaches zero.[12] The rate of QST is given by
As compared to  the absence of summation over n, which represent
different above threshold ionization (ATI) peaks, is remarkable.

Strong field approximation for the ionization

rate[edit]
The calculations of PPT are done in the E-gauge, meaning that the
laser field is taken as electromagnetic waves. The ionization rate can
also be calculated in A-gauge, which emphasizes the particle nature
of light (absorbing multiple photons during ionization). This approach
was adopted by Krainov model[13] based on the earlier works of
Faisal[14] and Reiss.[15] The resulting rate is given by
where,  is the minimum number of photons necessary to ionize
the atom, ,  (  is the ponderomotive energy),  is the double Bessel
function,,  where  is the angle between the momentum of the
electron, p, and the electric field of the laser, F, and, the
symbol FT denotes the three-dimensional Fourier transformation.
Finally,  incorporates the Coulomb correction in the SFA model.
Atomic stabilization/population trapping[edit]
In calculating the rate of MPI of atoms only transitions to the
continuum states are considered. Such an approximation is
acceptable as long as there is no multiphoton resonance between
the ground state and some excited states. However, in real
situation of interaction with pulsed lasers, during the evolution of
laser intensity, due to different Stark shift of the ground and
excited states there is a possibility that some excited state go into
multiphoton resonance with the ground state. Within the dressed
atom picture, the ground state dressed by  photons and the
resonant state undergo an avoided crossing at the resonance
intensity . The minimum distance, , at the avoided crossing is
proportional to the generalized Rabi frequency,  coupling the two
states. According to Story et al.,[16] the probability of remaining in
the ground state, , is given by
where  is the time-dependent energy difference between the
two dressed states. In interaction with a short pulse, if the
dynamic resonance is reached in the rising or the falling part of
the pulse, the population practically remains in the ground
state and the effect of multiphoton resonances may be
neglected. However, if the states go onto resonance at the
peak of the pulse, where , then the excited state is populated.
After being populated, since the ionization potential of the
excited state is small, it is expected that the electron will be
instantly ionized.
In 1992, de Boer and Muller [17] showed that Xe atoms
subjected to short laser pulses could survive in the highly
excited states 4f, 5f, and 6f . These states were believed to
have been excited by the dynamic Stark shift of the levels into
multiphoton resonance with the field during the rising part of
the laser pulse. Subsequent evolution of the laser pulse did
not ionize completely these states leaving behind some highly
excited atoms. We shall refer to this phenomenon as
"population trapping".

Schematic presentation of lambda type population trapping. G is the ground

state of the atom. 1 and 2 are two degenerate excited states. After the
population is transferred to the states due to multiphoton resonance, these
states are coupled through continuum c and the population is trapped in the
superposition of these states.
We mention the theoretical calculation that incomplete
ionization occurs whenever there is parallel resonant excitation
into a common level with ionization loss.[18] We consider a state
such as 6f of Xe which consists of 7 quasi-degnerate levels in
the range of the laser bandwidth. These levels along with the
continuum constitute a lambda system. The mechanism of the
lambda type trapping is schematically presented in figure. At
the rising part of the pulse (a) the excited state (with two
degenerate levels 1 and 2) are not in multiphoton resonance
with the ground state. The electron is ionized through
multiphoton coupling with the continuum. As the intensity of
the pulse is increased the excited state and the continuum are
shifted in energy due to the Stark shift. At the peak of the
pulse (b) the excited states go into multiphoton resonance with
the ground state. As the intensity starts to decrease (c), the
two state are coupled through continuum and the population is
trapped in a coherent superposition of the two states. Under
subsequent action of the same pulse, due to interference in
the transition amplitudes of the lambda system, the field
cannot ionize the population completely and a fraction of the
population will be trapped in a coherent superposition of the
quasi degenerate levels. According to this explanation the
states with higher angular momentum- with more sublevels-
would have a higher probability of trapping the population. In
general the strength of the trapping will be determined by the
strength of the two photon coupling between the quasi-
degenerate levels via the continuum.In 1996, using the very
stable laser and by minimizing the masking effects of the focal
region expansion with increasing intensity, Talebpour et al.
[19]
 observed structures on the curves of singly charged ions of
Xe, Kr and Ar. These structures were attributed to electron
trapping in the strong laser field. A more unambiguous
demonstration of population trapping has been reported by T.
Morishita and C. D. Lin.[20]
Non-sequential multiple ionization[edit]
The phenomenon of non-sequential ionization (NSI) of atoms
exposed to intense laser fields has been a subject of many
theoretical and experimental studies since 1983. The
pioneering work began with the observation of a “knee”
structure on the Xe2+ ion signal versus intensity curve by
L’Huillier et al.[21] From the experimental point of view, the NS
double ionization refers to processes which somehow enhance
the rate of production of doubly charged ions by a huge factor
at intensities below the saturation intensity of the singly
charged ion. Many, on the other hand, prefer to define the NSI
as a process by which two electrons are ionized nearly
simultaneously. This definition implies that apart from the
sequential channel  there is another channel  which is the
main contribution to the production of doubly charged ions at
lower intensities. The first observation of triple NSI
in argon interacting with a 1 µm laser was reported by Augst et
al.[22] Later, systematically studying the NSI of all rare gas
atoms, the quadruple NSI of Xe was observed.[23] The most
important conclusion of this study was the observation of the
following relation between the rate of NSI to any charge state
and the rate of tunnel ionization (predicted by the ADK
formula) to the previous charge states;
where  is the rate of quasi-static tunneling to i'th charge
state and  are some constants depending on the
wavelength of the laser (but not on the pulse duration).
Two models have been proposed to explain the non-
sequential ionization; the shake-off model and electron re-
scattering model. The shake-off (SO) model, first proposed
by Fittinghoff et al.,[24] is adopted from the field of ionization
of atoms by X rays and electron projectiles where the SO
process is one of the major mechanisms responsible for
the multiple ionization of atoms. The SO model describes
the NS process as a mechanism where one electron is
ionized by the laser field and the departure of this electron
is so rapid that the remaining electrons do not have
enough time to adjust themselves to the new energy
states. Therefore, there is a certain probability that, after
the ionization of the first electron, a second electron is
excited to states with higher energy (shake-up) or even
ionized (shake-off). We should mention that, until now,
there has been no quantitative calculation based on the
SO model, and the model is still qualitative.
The electron rescattering model was independently
developed by Kuchiev,[25] Schafer et al,[26] Corkum,[27] Becker
and Faisal[28] and Faisal and Becker.[29] The principal
features of the model can be understood easily from
Corkum's version. Corkum's model describes the NS
ionization as a process whereby an electron is tunnel
ionized. The electron then interacts with the laser field
where it is accelerated away from the nuclear core. If the
electron has been ionized at an appropriate phase of the
field, it will pass by the position of the remaining ion half a
cycle later, where it can free an additional electron by
electron impact. Only half of the time the electron is
released with the appropriate phase and the other half it
never return to the nuclear core. The maximum kinetic
energy that the returning electron can have is 3.17 times
the ponderomotive potential () of the laser. Corkum's
model places a cut-off limit on the minimum intensity ( is
proportional to intensity) where ionization due to re-
scattering can occur.

Feynman diagram for the process of double ionization in an atom through

re-scattering mechanism

The re-scattering model in Kuchiev's version (Kuchiev's

model) is quantum mechanical. The basic idea of the
model is illustrated by Feynman diagrams in figure a. First
both electrons are in the ground state of an atom. The lines
marked a and b describe the corresponding atomic states.
Then the electron a is ionized. The beginning of the
ionization process is shown by the intersection with a
sloped dashed line. where the MPI occurs. The
propagation of the ionized electron in the laser field, during
which it absorbs other photons (ATI), is shown by the full
thick line. The collision of this electron with the parent
atomic ion is shown by a vertical dotted line representing
the Coulomb interaction between the electrons. The state
marked with c describes the ion excitation to a discrete or
continuum state. Figure b describes the exchange process.
Kuchiev's model, contrary to Corkum's model, does not
predict any threshold intensity for the occurrence of NS
ionization.
Kuciev did not include the Coulomb effects on the
dynamics of the ionized electron. This resulted in the
underestimation of the double ionization rate by a huge
factor. Obviously, in the approach of Becker and Faisal
(which is equivalent to Kuchiev's model in spirit), this
drawback does not exist. In fact, their model is more exact
and does not suffer from the large number of
approximations made by Kuchiev. Their calculation results
perfectly fit with the experimental results of Walker et al.
[30]
 Becker and Faisal[31] have been able to fit the
experimental results on the multiple NSI of rare gas atoms
using their model. As a result, the electron re-scattering
can be taken as the main mechanism for the occurrence of
the NSI process.
Multiphoton ionization of inner-valence
electrons and fragmentation of polyatomic
molecules[edit]
The ionization of inner valance electrons are responsible
for the fragmentation of polyatomic molecules in strong
laser fields. According to a qualitative model [32][33] the
dissociation of the molecules occurs through a three-step
mechanism:

 MPI of electrons from the inner orbitals of the molecule

which results in a molecular ion in ro-vibrational levels of an
excited electronic state;
 Rapid radiationless transition to the high-lying ro-vibrational
levels of a lower electronic state; and
 Subsequent dissociation of the ion to different fragments
through various fragmentation channels.
The short pulse induced molecular fragmentation may be
used as an ion source for high performance mass
spectroscopy. The selectivity provided by a short pulse
based source is superior to that expected when using the
conventional electron ionization based sources, in
particular when the identification of optical isomers is
required.[34][35]

Kramers-Henneberger frame and

ionization phase effects[edit]
Studying the strong field ionization of the atom in so called
Kramers-Henneberger (K-H) frame[36] leads to the
conclusion that the ionization efficiency strongly depends
on the temporal details of the ionizing pulse but not
necessarily on the field strength and the total energy of the
ionizing pulse pumped into the atom.[37] The Kramers-
Henneberger frame is the non-intertial frame moving with
the free electron under the influence of the harmonic laser
pulse. The free electron solution of the Newton equations
for the electron in one dimension in the harmonic laser field
will be also harmonic
The frame comoving with this electron will be
obtained by the coordinate transformation
while the added Coulomb potential will be
The full cycle time-average of that potential
which is
will be the even function of  and
therefore having the maximum at  while
for that initial condition the solution will
be  in the K-H and it will be therefore
identical to the free electron solution in
the laboratory frame. The electron
velocity on the other hand is phase
shifted both to the field strength and to
the electron position:
Therefore, considering
the wavelet pulses and defining the
ionization as the full escape from the
line segment of the length 2r (or from
the spherical region in three
dimensions) the full ionization
happens in the classical model after
the time  or no ionization at all
depending if the harmonic field
wavelet is cut at the zero minimum or
the maximum velocity.

Dissociation –
distinction[edit]
A substance may dissociate without
necessarily producing ions. As an
example, the molecules of table
sugar dissociate in water (sugar is
dissolved) but exist as intact neutral
entities. Another subtle event is the
dissociation of sodium chloride (table
salt) into sodium and chlorine ions.
Although it may seem as a case of
ionization, in reality the ions already
exist within the crystal lattice. When
salt is dissociated, its constituent
ions are simply surrounded by water
molecules and their effects are
visible (e.g. the solution
becomes electrolytic). However, no
transfer or displacement of electrons
occurs. Actually, the chemical
synthesis of salt involves ionization.
This is a chemical reaction.

See also[edit]
 Above threshold ionization
 Ionization chamber – Instrument for
detecting gaseous ionization, used
in ionizing radiation measurements
 Ion source
 Photoionization
 Thermal ionization
 Electron ionization
 Chemical ionization
 Townsend avalanche – The chain
reaction of ionization occurring in a
gas with an applied electric field

Phase transitions of matter (

 v
 t
 e
)

To

Plas
Solid Liquid Gas
ma

Soli Meltin Sublim

d g ation

Liqu Freez Vaporiz

id ing ation
Fr
o Conde Ioniz
Depo
m Gas nsatio atio
sition
n n

Recom
Plas
binatio
ma
n