249

Chapter 3

FROM MULTIPHOTON TO TUNNEL IONIZATION


S. L. CHIN
Canada Research Chair (Senior)
Center for Optics, Photonics and Laser &
Department of Physics, Engineering Physics and Optics
Laval University, Quebec City,
Quebec, G1K 7P4, Canada
slchin@phy.ulaval.ca


The story of the development of multiphton ionization to tunnel
ionization is told briefly from the experimental point of view. It stresses
the physical idea of tunneling ionization and the practical use of some
tunneling formulae to fit experimental data. ADK formula is not
universally valid in spite of its popularity.



Contents

1. Introduction 250
2. Laser Induced Breakdown 251
3. Multiphoton Ionization of Atoms (19641978) 253
4. A Persistent Challenge in the 1960s and 1970s: Tunnel Ionization 254
5. Some Surprises (19791989) 254
6. Tunnel Ionization using Long and Short Wavelength Lasers 261
7. Which Tunnel Ionization Formula to Use? 263
Conclusion 269
Acknowledgments 269
References 269




250

1. Introduction

This is a personal account of the progress of high laser field physics in atoms and
molecules. The author has experienced the entire development of this field of
research from the very beginning of Q-switched laser induced breakdown of
gases, multiphoton ionization (MPI) and tunnel ionization of atoms and
molecules that continues into the current state of the control of molecules in
ultrafast intense laser field, atto-second laser science, etc. The purpose of this
review is to tell a brief story of the development from laser induced breakdown
through multiphoton ionization to tunnel ionization. Emphasis will be given to:
(1) the physics of tunnel ionization based on our experimental results using a CO
2

laser; (2) the applicability of the concept of tunneling to ionization of atoms and
molecules using intense femtosecond near i.r. laser pulses.
We shall begin discussing the physics of laser-induced breakdown of gases
in the early 1960s. The development of multiphoton ionization follows. There
was a seemingly conceptual bottleneck towards the end of the 1970s when
multiphoton ionization physics was thoroughly studied. While laser technology
has raised the intensity higher and higher in the laboratory so that strong field
effect should be observable, many did not yet accept the concept of tunnel
ionization even though it has been proposed by Keldysh in 1964.
36
One reason
was probably because there was so far no experimental evidence of tunnel
ionization. The author and his co-workers first confirmed experimentally the
existence of tunnel ionization in the mid-1980s using a CO
2
laser. The concept of
tunnel ionization eventually becomes a doorway concept in modern strong field
physics and chemistry.
Meanwhile, many surprisingly new and unexpected high field phenomena
were discovered. They include above threshold ionization (ATI), high order
harmonic generation and multiple ionization. The latter naturally led to the
question of sequential and non-sequential ionization. In molecules, many new
concepts were proposed and confirmed experimentally using intense femtosecond
laser pulses: bond softening and hardening, above threshold dissociation, charge
resonance enhanced ionization, Coulomb explosion, etc. Most of these
phenomena are based on tunnel ionization as the first step of the physical
processes. The author will not go into any of the details of these phenomena
except for ATI and multiple ionization.
Parallel to the modern development of high laser field physics and
chemistry, the propagation of intense femtosecond laser pulses in transparent
optical media leads to self-focusing and filamentation. Filament as long as km
piercing through the atmosphere was indicated by new experiments. Essentially,
a qualitative picture is the following. A powerful near i.r (we have in mind the
most popular 800 nm Ti-sapphire laser) femtosecond laser pulse self-transforms
into a self-organizing light bullet (Chin et al.
22
) becoming a white light laser



251

pulse whose spectral width covers the whole visible region while propagating in
many kinds of optical media (air, water, glass, etc.). The broad spectrum extends
into the i.r. to about 4 microns in the case of air. This would mean that the
original amplitude and phase of the laser pulse, after propagating through any
optical medium including air, would be changed dramatically due to self-phase
modulation and self-steepening. No interaction system in any practical
experiment would be able to avoid this eventual modification of the lasers
amplitude and phase when the pulse propagates through at least the optical
window of the system. No systematic study on this effect is yet published while
preliminary experiments in our laboratory show some important consequences, in
particular, that due to self-focusing, pulse splitting, intensity clamping, etc. while
the pulse propagates through the window of the interaction system. This
propagation effect on strong field interaction will not be discussed. Interested
readers on the physics of propagation are referred to the following papers and
references therein (Chin et al.
21
; Kandidov et al.
35
)
Much of the story to be told is based on the authors personal experience
and is thus rather subjective. Nevertheless, he tries as much as possible to give a
just account of some of the important milestones in experimental strong laser
field physics.


2. Laser Induced Breakdown

Soon after its invention around 1963, the Q-switched ruby laser has created some
huge surprises. It could generate hot plasmas when focused onto solid targets. This
sparked the beginning of the construction of big national laser laboratories to do
laser plasma research with the aim of achieving laser induced nuclear fusion in
many countries. (The author will not talk about this event in this paper.) In the
meantime, Meyerand and Haught
43
observed that a Q-switched ruby laser pulse
could even generate a spark (electrical discharge) in air. This so-called laser
induced breakdown of air (gases) started the era of multiphoton physics. It was
recognized that the spark involved the strong ionization of the air molecules. The
surprise at that time was that the laser photon energy from a Q-switched ruby laser
(1.78 eV) was much smaller than the ionization potentials of air molecules
(oxygen: 12.1 eV and nitrogen: 15.6 eV). It was inconceivable that there could be
any photoelectric effect by absorbing one photon and ionizing the molecules. The
idea of multiphoton absorption was thus developed even though the theory of two-
photon absorption was already published in 1931 by Goeppert-Mayer.
33
After a lot
of extensive theoretical and experimental work in many laboratories, it was finally
proposed that optical breakdown of gases followed essentially a three-step process
(Fig. 1). (1) Multiphoton ionization of impurity molecules with low ionization
potentials would easily provide a few free electrons with low initial kinetic energy
in the focal volume at the front part of the pulse.
12
(2) The free electrons in the



252

strong laser field could absorb n photons (n = 0, 1, 2, 3, ) while colliding
(scattering) with a much heavier particle (atom, molecule or ion). The heavy
particle is to conserve momentum during the interaction. This process is called
inverse Bremsstrahlung or freefree transition. (3) After one or more inverse
Bremsstrahlung processes, the free electron would acquire a kinetic energy E
e

higher than the ionization potential of the gas molecule/atom. Subsequent collision
would give rise to the ejection of an extra electron from the molecule/atom. This
would result in two low energy electrons. They would undergo the same processes
as before each giving rise to two electrons, and so on until the gas is fully ionized.
This is called cascade or avalanche ionization; i.e. breakdown.
44


Fig.1. Visualization of laser induced breakdown.


Many experiments were performed to verify the cascade ionization process.
44

The fundamental process of the initiation of breakdown by the MPI of impurities
was proved experimentally by the author
12
whereas the freefree transition which
is at the center of cascade ionization was observed by Weingartshofer.
51,52

The initiation process of cascade breakdown, namely MPI, had its own
physical interest because it touches upon a question of fundamental importance,
i.e. the absorption of more than one photon by an atom or a molecule.



253

3. Multiphoton Ionization of Atoms (19641978)

There are already many papers and books describing the physics of MPI,
including the current series of books. (See for example Chin and Lambropoulos,
15

Delone and Krainov
23
and references therein). Essentially, the time dependent
perturbation theory can explain all the experimental observations using ns and ps
laser pulses. The author would like to point out a few historical milestones in the
pursuit of the understanding of MPI physics.
19631964: Keldysh
36
published the paper on the theory of ionization of
atoms in a strong laser field. He coined a parameter that separates the regimes
of MPI and tunnel ionization where
0
2

E
F
(in atomic units)
where is the laser frequency, F the laser electric field strength and E
0
, the
ionization potential of the atom.
It was concluded that when << 1, tunnel ionization prevails while when
>> 1, it is a multiphoton effect. The multiphoton effect means that the physics
of interaction can be explained by the perturbation theory (Chin and
Lambropoulos
15
and references therein).
1960s1980s: In the 1960s till the early 1980s, only the condition of >> 1
was satisfied in all experiments using long (ns or sub-ns) pulses. The following
lists the various contributions to MPI physics from the experimental point of
view.
Delones first experiment on MPI (19641965).
49

Mainfrays major contribution to the field from the beginning of MPI soon after
Delone et al.s work till his retirement in 19961997: this includes MPI physics,
resonance effect, coherence effect, pulse length effect
42
leading to ATI and HHG
(see later).
Chin and Isenors
13
observation and interpretation of the saturation of
ionization in the center of the focal volume
11
: this was not a trivial conclusion
because it was difficult to conceive that such a high order nonlinear process could
have reached a probability of ionization of unity (i.e. saturation) so that the
neutral atoms in the most intense part (usually center) of the focal volume are
depleted. The consequence is the now famous slope of 3/2 in the loglog plot of
ion yield vs laser peak intensity. This later conclusion was due to Cervenon and
Isenor.
10

The authors first experiment on the MPI of polyatomic molecules
14
: it was
natural to extend multiphoton ionization to molecules and indeed both ionization
and fragmentation were observed. Chemists later expanded into the now well-
known branch of laser chemistry.



254

Weingartshofer first made the direct observation of free-free transition
51
: this
was a very important experiment demonstrating the fundamental interaction
process of the absorption/emission of one or more entire photons by a free
electron in the vicinity of a much heavier particle (atom, molecule or ion) in the
presence of a strong radiation field. In this process, the conservation of
momentum through the implication of the much heavier particle is the key to
inducing the absorption or emission of photons. This is distinct from the
Compton process in which an electron is scattered by a photon resulting in the
change of kinetic energy of the electron by a fraction of the photon energy while
the photons frequency is changed.

The consequence of many studies in the field of MPI towards the end of the
1970s led to applications such as REMPI (resonance MPI), laser isotope
separation and in a general sense, laser chemistry. At that time, it was believed
that the fundamental physics of MPI was well-understood, for e.g. the I
n
law of
MPI, the theoretically expected coherence effect on MPI, resonance effect,
saturation, pulse length effect, etc. (cf. Chin and Lambropoulos
15
and references
therein). So, what could be new?


4. A Persistent Challenge in the 1960s and 1970s: Tunnel
Ionization

Is tunnel ionization possible in the field of high optical frequency? Can one
experimentally reach the condition of << 1? Keldyshs paper certainly has
inspired a huge amount of discussion right from the beginning of the MPI era. It
inspired also the theoretical papers written by Faisal
26
and Reiss
48
which initially
were not accepted as being valid physically by many MPI practitioners. (The trio
was later referred to as the KFR theory.) There had been attempts to observe
experimentally tunnel ionization of atoms by the French Saclay group in the
1970s. But the results were negative (Lompr et al.
41
). This reinforced the
thinking that tunnel ionization, though possible in the case of DC field ionization,
would be too difficult to be observed if not totally impossible. An early account
of the attempt to observe tunnel ionization is given by the author in Chin and
Lambropoulos,
15
Chapter 1.


5. Some Surprises (19791989)

Similar to many other scientific advancement, it was mostly, if not always, by
accident and not by design that the advancement of the field of MPI was
developed. The following gives an account of some of the most important
developments.



255

5.1. Above threshold ionization (ATI) observed by the Saclay group
led by Mainfray

Towards the second half of the 1970s, Mainfray realized that the experimental
study of MPI by measuring only the ion yield is already mature in the sense that
not many new things could be observed (Mainfray, private communication).
Since in the interaction of a strong radiation field with atoms, the product of the
interaction consists of ions, electrons and photons, Mainfray believed that one
should try to look at the electrons and the photons. He led his group to do exactly
this and the unexpected phenomena of above threshold ionization or ATI
1
and
high order harmonic generation (HHG) were discovered.
40

The observation of the absorption of many more photons by the ionized
electron in the continuum (ATI) was initially counter intuitive. How could an
electron in the continuum (i.e. free electron) absorb photons? Should it not be
similar to the Compton effect where entire photon could not be absorbed? Very
soon, it was recognized that the concept of an electron in the continuum has to be
carefully defined. The electron raised into the continuum by MPI is not yet free.
MPI leads to an almost instantaneous excitation (in the limit of the uncertainty
principle) of a bound electron to the continuum. However, geometrically
speaking, it is very similar to the FrankCondon transition in molecular
absorption of radiation. The electron that is excited into the energy continuum
energetically speaking is still in its original vicinity of the nucleus. Moreover, it is
bathed in the strong electromagnetic field (i.e. in a dressed state or Volkov state).
When it starts to move away from this original position towards infinity, the
electron would have the probability to absorb more photons in the strong laser
field very similar to free-free transition. In fact, it was described by
Kupersztych
37
as half-inverse Bremsstrahlung or half freefree transition because
the electron starts to move out from around the vicinity of the nucleus. Hence, its
kinetic energy spectrum shows up as peaks spaced by one photon energy very
similar to the experimental results of freefree transition done by
Weingartshofer.
51

It turns out later that this phenomenon of ATI is intimately related to non-
sequential ionization and high order harmonic generation. The semi-classical
electron re-scattering model in the tunneling regime (Kuchiev 1986, Corkum
1994, Kulander et al. 1993, van Linden van den Heuvell 1988, Gallagher 1988)
could explain a lot of observation todate. (See review by DiMauro and
Agostini.
24
) Today, ATI is put to excellent use in the detection of the absolute
phase of intense few cycle laser pulses.
45,9


5.2. Double and multiple ionization

Double ionization in MPI of rare earth atoms (two electron systems) was first
observed by Aleksakhin et al.
2,3
In the era when multiphoton ionization of one



256

single electron was considered highly improbable, the ejection of two electrons
was certainly a rarity. It was in this work that the question of how the two
electrons were ejected whether sequentially or simultaneously (non-sequential
ionization) was first discussed. Similar work by Feldmann et al.
30
followed.
Later, in the French Saclay group led by Mainfray, the first sign of non-
sequential ionization of Xe
2+
was observed by LHuillier et al.
39
They also
observed multiply-charged ions of up to Xe
4+
. It turned out that so long as the
laser intensity keeps increasing with the advancement of the laser technology,
one can almost indefinitely increase the multiply-charged state of an ion and no
limit is in sight yet. Thus, later in the 1980s, up to Xe
6+
could be measured using
a CO
2
laser.
17
Using the newly developed TW level CPA laser in the laboratory
of Mourou at the University of Rochester, the author and co-workers were able to
measure up to Xe
12+
(Fig. 2). (See also Augst et al.
5,6
) The most recent
experiment from the JAERI Laboratory in Japan observed up to Xe
26+
using
100TW femtosecond Ti-sapphire laser pulses.
53


Xe Xe (8+ 7+ 6+ 5+ 4+ 3+ 2+ 1+)
Time-of-flight mass spectrum (unpublished)
The following publications were based upon such spectra: S. Augst et al,
PRL, 63,2212-2215(1989); S. Augst et al, JOSA-B, 8,858-867(1991).
1
st
result on multiple ionization of Xe using the 1
st
T
3
laser by S. Augst, D. Strickland, S.
L. Chin, J. H. Eberly & G. Mourou (1988, Rochester, NY)
Even Xe (12+)

Fig. 2. Using the first T3 laser at 1.06 microns wavelength in the University of
Rochesters Laboratory for Laser Energetics to ionize Xe resulting in multiply-charged
states of up to Xe12+.



257

5.3. High order harmonic generation

The TW level CPA laser used in the Saclay laboratory led by Mainfray produced
another surprise; i.e. the now well-known higher order harmonics generation was
observed. The physics of the relatively very efficient generation of high
harmonics is again based upon the re-scattering theory (Kuchiev 1986, Corkum
1994, Kulander et al. 1993) and will not be discussed further here.

5.4. Tunnel ionization

As mentioned above, tunnel ionization was considered by many to be almost
impossible before the mid-1980s. The authors first experimental observation of
the existence of tunnel ionization of Xe atoms using a CO
2
laser in 1985 was
indeed a surprise.
16
The experimental condition satisfied Keldyshs condition of
<< 1 and the results are unambiguous. More surprising was the observation of
Xe
2+
and Xe
3+
but now under the condition of < 1. Preceding this observation,
Farkas and the author have already observed tunnel ejection of electrons from a
gold surface
28,29
using a CO
2
laser.
Meanwhile, Delone and co-workers in the Soviet Union were also
attempting the same experiment. Unfortunately, while they were preparing the
experiment, the author had already published the first observation. Since then,
they did not complete the experiments. (The above was described to the author by
one of his co-workers, Dr. F A Ilkov, who was responsible for setting up the
experiment.) Later, they did the calculation by adopting an improved form of the
Keldysh formula that was due to Perelomov et al.
46
for the ionization of a
hydrogen atom. The ionization rate of an arbitrary state of a hydrogen atom is
given by:
( )
]
]
]
,

]
]
]
,

,
(
(
,
\
,
,
(
j

F
F
F
F
F
F
E m l f C w
m n
l n
3
2
exp
2

3
,
0
1 2
0
2
1
0
0 ,
(1)
where ( )
2
3
0 0
2E F and
0
E = ionization potential. The factor
(
(
,
\
,
,
(
j
0

3
F
F
is a result
of averaging the rate over one cycle of the field.
n
F
F
2
0
2
(
,
\
,
(
j
is the long range effect
of the Coulomb potential; C
n,l
and f (l, m) contain in formation of the initial
atomic state.
The scope of the above formula was extended by Ammosov, Delone and
Krainov
4
by replacing the hydrogen n,l by the effective quantum numbers n* and



258

l* and approximating the coefficient C
n,l
by a simple expression using the quasi-
classical approximation for n* >> 1.
The resulting formula became a simpler one. In the original paper, there
were a number of misprints. The following is the corrected ADK formula which
was due to Ilkov, Decker and Chin
34
:

( ) ]
]
]
]
,
,

]
]
]
]
,
,

,

+
(
,
\
,
(
j

F n
Z
F n n
eZ
n
l
n
Z e
w
n
3 *
3
2
3 * *
3
* 3 *
2
3
2
exp
1 2
4
1 2
1 2
3

3
2
3
*
2
3
(2)
e = 0.71828 , Z is the ionic charge, F the electric field strength of the laser; l
the orbital angular momentum quantum number, and n* the effective principal
number =
0
2E
Z
.
This formula remains valid down to n* ~ 1. This allowed the modified
formula (1) to be applied to more complex atomic/ionic systems. Equation (2) is
the result of this development for the case of m = 0 where m is the magnetic
quantum number, the other terms with m = 1, 2, 3, being negligibly small
in comparison to the case when F
0
/F >> 1. The above formulae are valid for
linear polarization.
The ADK
4
formula (Eq. (2)) fits very well the authors first experimental
observation of tunnel ionization of Xe atoms.
16
The authors continued
experimental study of tunnel ionization using the CO
2
laser (including the first
observation of tunnel ionization of molecules
18
) led to significant advancement in
the understanding of the process. For example, simple molecules with no i.r.
vibrational resonance behave like atoms. In fact, all atoms and non-resonant
molecules can be tunnel ionized by the CO
2
laser radiation and are very well
described by the ADK formula. For example, the ADK formula (Eq. (2)) fits
nicely the experimental data obtained in the authors laboratory using a CO
2

laser
50
to ionize Xe, Kr, Ar, H
2
, O
2
, N
2
, CO, CO
2
, and NO. Figures 3 and 4 show
two examples of tunnel ionization, one of multiple ionization of Xe (Fig. 3) and
one of Kr as compared to CO (with almost equal ionization potentials, 13.99 eV
for Kr and 14.01 eV for CO) (Fig. 4). The fit of the ADK formula without using
any adjustable parameter is excellent. We note that they are all under the
condition of < 1/2 instead of << 1 as required by the Keldysh theory (Walsh,
et al.
50
and references there-in).
The reason is explained in what follows. We recall first the definition of
36


0
2

E
F
(in atomic units) (3)
It was derived from the following consideration. Referring to Fig. 5, the ease or
difficulty of tunneling can be expressed as the ratio between the equivalent
classical time it takes for the electron to tunnel out the potential barrier while the



259

potential is bent down. This ratio is called . Since the potential is bent down
during half a cycle of the field oscillation, the ratio can be expressed as

L
T

cycle laser
time tunnelling
2
1
2
1
(4)
where
T
tunneling time = classical time of flight of an electron through a
potential barrier, and
L
period of laser field oscillation 1/.
Note that is simply the field oscillation frequency and not the circular
frequency. We can calculate the classical time of flight of an electron through the
potential barrier shown in Fig. 5 according to Keldysh
36
:

T
= "tunneling distance" / "tunneling speed" .




Fig. 3. CO
2
laser tunnel ionization
of Xe. The ADK tunneling formula
is used to fit the data without any
adjustable parameter.

Fig. 4. CO
2
laser tunnel ionization of Kr
and CO. Both have similar ionization
potentials. The total overlap of the ion
yield indicates that CO behaves as if it
were an atom. The ADK tunneling formula
is used to fit the data without any
adjustable parameter.




260

r
r
o
R
c
-r
o
|V(r)|<Fr
E
|V(r)|<Fr |V(r)|>Fr
V(r)
-Fr
V(r)-Fr
-E
i
tunnel ionization

Fig. 5. Schematic diagram of tunnel ionization.


Assume that the electron in the classical Coulomb potential well moves
back and forth along a one-dimensional axis r (Fig. 5) with a kinetic energy equal
to the ionization potential E
0
before the external field is applied. Its speed of
motion is thus

2
1
0
2
(
,
\
,
(
j

m
E
v (5)
where m is the electron mass. When the external field is applied, the electron
would "pass" through the potential barrier with this speed through the "tunneling
distance" R
c
assuming that the electron starts to move out of the barrier ar r = 0.
R
c
= E
0
/ eF
where e is the electron charge, and F is the field strength.
( )
2 / 1
0
2
1
2
1
2

mE
eF
L
v
R
L
T
c

261

or in atomic units (e = m = 1)
( )
2 / 1
0
2

E
F

which is Eq. (3). The experimentally found condition of <1/2 means that the
tunneling time is less than of the laser fields period (see Eq. (4)). This is
reasonable because as shown in Fig. 5, the Coulomb potential of the electron is
bent down on one side of the Coulomb potential well during of a period and
during most of this half period, the barrier is too large for the electron to go
through.
Obviously, the concept of tunnel ionization does not take into account the
influence of the intermediate states although the latter does play a role as in the
case of the theory of multiphoton ionization based upon the perturbation theory
(Geltman,
31
Gold and Bebb
32
; more references can be found in Chin and
Lambropoulos
15
). To explain this, one recognizes that the coupling between the
ground state and any excited state of an atom or molecule (meaning the existence
of an excited state) would take some time to develop. This time is at least one
cycle of the field oscillation from the quantum mechanical point of view because
the transition (coupling) probability is obtained by integrating the transition
matrix over time over at least one cycle of the laser oscillation. In a time less than
one cycle of oscillation, such a coupling could be negligible or meaningless.
Since the experimentally observed condition for tunnel ionization to occur is
< ; i.e. the tunneling time is smaller than of the field oscillation, there is no
need to consider the influence of intermediate states.
20

The concept of tunnel ionization was finally accepted by most in the strong
laser field community since 1993 as was evidenced by the transformation of the
mentality during the 1993 International Conference on Multiphoton Processes
held in Quebec City, Canada.
25



6. Tunnel Ionization using Long and Short
Wavelength Lasers

It is recognized by now that using nanosecond CO
2
laser pulses (wavelength
around 10 microns, one photon energy around 0.1 eV), ionization of atoms and
molecules is always due to tunneling.
16,18,50
There is practically no chance for
multiphoton ionization to occur in any significant way because multiphoton
ionization of any atom or molecule would imply the simultaneous absorption of
nearly or more than 100 photons. This would require, in principle, a huge
intensity. Before this happens, tunneling takes over. Thus, using the CO
2
laser,
there is an advantage to observe "clean" tunnel ionization.
In the case of using near i.r. or visible wavelength (photon energy around 1
to 4 eV) laser pulses with long duration (nanosecond to tens of picoseconds), the



262

rising and the falling parts of the laser pulse would contribute significantly to
MPI even if the peak intensity is higher than that which satisfies the tunnel
ionization condition. The total ion yield due to tunnel ionization by the peak
intensity would thus be masked by this MPI event at the rising/falling parts of the
pulse. If the long pulses peak intensity is much higher than the intensity for
tunnel ionization (i.e. << 1), the integrated effect of MPI at the rising part of the
pulse would be enough to almost totally ionize the atom. Thus, before the pulses
intensity reaches the regime of tunnel ionization, there are no more neutral atoms
left to interact with the high intensity part of the pulse. The ion that is left over
would have a higher ionization potential; i.e. >> 1, and MPI would prevail
again. This probably was the reason why using a 30 ps, 1 micron wavelength
laser pulse whose peak intensity gave a value less than 1, the French Saclay
group did not observe any clear tunneling signal in the ionization of helium.
41

Using the long (ns) CO
2
laser pulse, the rising/falling parts would not contribute
to any significant MPI process because it requires more than 100 photons
absorption and the probability is next to zero. When the pulse intensity reaches
the peak region where the intensity is high enough to satisfy the condition of
< 1/2, tunnel ionization turns on/off "suddenly" as if the pulse had very short
rise/fall times.
This leads to the question as to whether one could ever observe tunnel
ionization experimentally using near i.r. to near uv laser pulses. The answer lies
in the success of the CO
2
laser as mentioned in the preceding paragraph; i.e. if the
rise/fall times of the near i.r. to near u.v.laser pulses are fast enough so that MPI
in the rising/falling parts of the pulse is negligible because of the low intensity,
tunnel ionization would be observable at the peak region. With this thinking, one
could also conclude that the shorter the wavelength is the faster the rise time
should be for the neglect of MPI at the rising/falling parts of the pulse.
The above prediction is confirmed in recent years. Using femtosecond laser
pulses in the near i.r. to the visible regime, tunnel ionization seems to dominate
all the interaction physics of atomic or molecular ionization. Since about 1993,
almost all femtosecond laser (near i.r. to near uv) ionization work uses one form
or another of the tunneling theories to explain/fit the experimental results. Indeed,
almost all experimental work on the interaction of intense femtosecond lasers
(from near i.r. to near uv) with atoms and molecules leading to non-sequential
ionization, fragmentation, high order harmonic generation, above threshold
ionization, atto-second laser pulse generation, etc. start with the tunnel ionization
of the species before discussing the subsequent physics of interaction. Tunnel
ionization becomes the initiating process in all intense femtosecond laser
interaction physics that involves the ejection of electrons from atoms or
molecules; i.e. tunnel ionization becomes the doorway concept in modern
ultrafast intense laser science.





263

7. Which Tunnel Ionization Formula to Use?

The above analysis shows that when using very short laser pulses, it is legitimate
to use the tunneling concept to describe the phenomenon of ionizing atoms and
molecules. We now ask the question: which model or which tunneling formula
should one use? Most people seem to favor the ADK formula without analyzing
the suitability. The authors like to discuss this from the experimental point of
view.
We have done many careful experiments in recent years on the tunnel
ionization of atoms and molecules using intense 200 fs Ti-sapphire laser pulses.
We have fitted our experimental results using various models of tunnel
ionization. The ADK formula certainly could not fit most of the experimental
results. In fact, strictly speaking, it fits only the results of ionization of helium.
Two theories excellently fit our and many other experimental results. One is
what we called the ppt theory (Perelomov, Popov and Terentev
46
) and the other
is the S-matrix theory developed by Faisal and Becker.
27
Figures 610 show our
experimental results on the tunnel ionization of all rare gas atoms using 200 fs Ti-
sapphire laser pulses (800 nm central wavelength).
38
The ion yield is plotted
against both the peak intensity of the laser pulse (lower horizontal scale) and the
corresponding values of (upper horizontal scale). Several theories were used to
fit the experimental results. These include the strong field approximation (SFA)
48

theory, the ADK formula, the ppt model and Szokes theory.
47
One can see that
the ADK formula fits only in the range where < 0.5 in the cases of He and Ne;
i.e. in the higher intensity ranges. At the lower intensity ranges where > 0.5,
there is a deviation from the experimental data as we should expect. Now, in the
cases of the other rare gas atoms, namely, Ar, Kr and Xe, the fit of the ADK
formula is way off since before < 0.5 is reached, saturation of the ion yield is
reached. In this saturation region, no interaction physics can be extracted even
though the ADK curve approaches the experimental data in the saturation region.
The SFA and the Szoke theories do not fit our experimental data either. Only the
ppt theory fits all the experimental data very well. The reason why the ppt theory
fits well the experimental results seems to come from its inclusion of the
Coulomb field effect on the outgoing electron during ionization.
Becker and Faisal
8
used their S-matrix theory
27
to fit our experimental data
and the fit was excellent.
From the experimental point of view, we could conclude that whenever one
wants to compare experimental data with the ADK theory, one must make sure
that the tunnel ionization condition of < 0.5 is satisfied. Otherwise, the fit could
only be considered as a qualitative guide. Many experimental data of this type
contain a lot of fluctuation (i.e. not as smooth as our data) and the dynamic range
of the yield spans over only 23 orders of magnitude, sometimes including the
saturation region. When such huge fluctuation points over such a small dynamic
range are fitted by the ADK formula in the region one or two orders of



264

magnitudes below the saturation point, the fit would look "not bad" as can be
imagined from the fit with the Xe or Kr data in Figs. 6 and 7.



Fig.6. Tunnel ionization of Xe using a Ti-sapphire laser
pulse at 800 nm/200 fs. Only the ppt theory fits well the
experimental data. ADK as well as other known theories
with analytical formulae could not fit the data.



265



Fig. 7. Tunnel ionization of Kr using a Ti-sapphire laser
pulse at 800 nm/200 fs. Only the ppt theory fits well the
experimental data. ADK as well as other known theories
with analytical formulae could not fit the data.




266



Fig. 8. Tunnel ionization of Ar using a Ti-sapphire laser
pulse at 800 nm/200 fs. Only the ppt theory fits well the
experimental data. ADK as well as other known theories
with analytical formulae could not fit the data.



267



Fig. 9. Tunnel ionization of Ne using a Ti-sapphire laser
pulse at 800 nm/200 fs. Only the ppt theory fits well the
experimental data. ADK formula starts to get closer to the
experimental data while other known theories with
analytical formulae could not fit the data.




268



Fig. 10. Tunnel ionization of He using a Ti-sapphire laser
pulse at 800 nm/200 fs. Both the ppt theory and the ADK
formula fit well the experimental data. No other known
theories with analytical formulae could fit the data.



269

Conclusion

The author has given a brief historical account on the experimental progress of
high field physics which is now taken up by chemistry extensively. The story
starts from the observation of laser induced breakdown to the extensive study of
the physics of multiphoton ionization. The theory of tunnel ionization was
predicted at the same time. However, the reality of the experiments prohibited the
observation of tunnel ionization easily. It takes a delay of more than 20 years
before such a phenomenon was confirmed in our laboratory using a CO
2
laser.
The advancement of laser technology permits experimentalists to use
femtosecond laser to ionize atoms and molecules and the short duration condition
of the laser pulse favors tunnel ionization. It was pointed out that care should be
taken in the use of tunnel ionization formula to fit with experimental data. The
ADK formula is good only under the condition of < . The better theories
would be the ppt theory and/or the S-matrix theory of Faisal and Becker.


Acknowledgment

This work was supported by NSERC, FQRNT (FCAR) and the Canada Research
Chairs.


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