Chemical and Dye Lasers

Chapter 10 by Orazio Svelto

Chapter 9 by Masamori-Endo-Robert
Online sources
Contents
Chemical Lasers:
• Introduction to chemical laser
• HF (hydrogen and fluoride) laser
• Chemical Oxygen-Iodine laser (COIL)
• Military applications of COIL

Dye Lasers:
• Rhodamine dye laser.
Chemical Laser
• A chemical laser is usually defined as one in which the population inversion is “directly” produced
by an exothermic chemical reaction.
• Chemical lasers usually involve either an associative or a dissociative chemical reaction between
gaseous elements.

1. An associative reaction can be described by an equation of the form A+B→ AB.

• For an exothermic reaction, some of the heat of reaction will appear as either rotational-vibrational
or electronic energy of the molecule AB. Thus, if a population inversion is achieved, the associative
reaction can in principle lead to either a vibrational-rotational or a vibronic transition.
• Inspite of much effort, however, only chemical lasers operating on vibrational-rotational transitions
have been demonstrated so far. For this kind of transition, the range of oscillation wavelengths,
achieved so far, lies between 3 and 10μm, with the HF and DF lasers being most notable examples.
Chemical Laser
2. A dissociative reaction, on the other hand, can be described by an equation of the general form
ABC → A+BC.
• If the reaction is exothermic, some of the heat of reaction can be left either as electronic energy of
the atomic species A or as internal energy of the molecular species BC. The most notable example
of a laser exploiting this type of reaction is the atomic iodine laser, in which iodine is chemically
excited to its 2𝑃1/2 state and laser action occurs between the 2𝑃1/2 state and the 2𝑃3/2 ground state
(λ=1.315 μm).
• Excited atomic iodine may be produced via the exothermic dissociation of 𝐶𝐻3 𝐼(or 𝐶𝐹3 𝐼, 𝐶3 𝐹7 𝐼),
the dissociation being produced by means of UV light (∼300 nm) from powerful flashlamps. More
recently, excited iodine has been produced via generation of excited molecular oxygen by reacting
molecular chlorine with hydrogen peroxide. The molecular oxygen, excited to its long-lived
singlet-state (the ground electronic state of oxygen molecule happens in fact to be a triplet state), in
turn transfers its energy to atomic iodine (oxygen-iodine chemical laser or chemical oxygen-iodine
laser ‘COIL’).
Importance of Chemical Lasers
• Chemical lasers are important mainly for two main reasons:
(1)They provide an interesting example of direct conversion of chemical
energy into electromagnetic energy.
(2)They are potentially able to provide either high output power (in cw
operation) or high output energy (in pulsed operation). This is
because the amount of energy available in an exothermic chemical
reaction is usually quite large.
HF Chemical Laser
• HF chemical lasers can be operated using either 𝑆𝐹6 or 𝐹2 as compounds donating the atomic
fluorine, and, from a practical view-point, the two lasers are very different.
• In commercial devices, the inert 𝑆𝐹6 molecule is used as fluorine donor and the gas mixture also
contains 𝐻2 and a large amount of He. An electrical discharge is then used to dissociate the 𝑆𝐹6 and
excite the reaction. The overall pressure of the mixture is around atmospheric pressure, the laser is
pulsed, and the laser configuration is very similar to that of a 𝐶𝑂2 TEA laser.
• The output energy of this type of device is, however, appreciably smaller than the input electrical
energy. Thus, the laser derives only a small part of its output energy from the energy of the
chemical reaction and it can only be considered marginally as a chemical laser.
• On the other hand, when a 𝐹2 and 𝐻2 gas mixture is used, the laser operates cw and it derives most
its power from the chemically reacting species. So, only the latter type of HF chemical laser will be
considered below.
Exciting Mechanism- Associative reaction
Elaboration of Inversion
• Atomic fluorine is then restored after this second reaction and this fluorine atom can then repeat
the same cycle of reaction, and so on. We thus have a classical chain-reaction which can result in a
large production of excited HF molecules.
• It should be noted that the heats of reaction of Eqs. (10.3.1) and (10.3.2) are 31.6 kcal/mole and 98
kcal/mole respectively, the two reactions being therefore referred to as the cold and hot reaction,
respectively.

Cold reaction:
• It should also be noted that, in the case of the cold reaction, the energy released, can easily be
shown to correspond to an energy of ∆𝐻 ≌ 1.372 𝑒𝑉 for each molecular HF produced.
• From the figure one thus sees that, if this were the only reaction, a population inversion would be
established, particularly for the (ν=2) → (ν=1) transition.
Elaboration of Inversion
Hot reaction:
• In the case of the hot reaction, on the other hand, excited HF up to the (ν=10) vibrational level can be
produced (Fig. 10.22b). The relative populations of these vibrational levels, N(ν) can be calculated and is also
shown in the same figure.
• One now sees that a pretty strong population inversion exists particularly for the (ν=5)→ (ν=4) transition.

(Optional)
• The reason why the HF molecule is left in an excited vibrational state, after chemical reaction, can be
understood in a simple way. Consider an F atom colliding with a 𝐻2 molecule. As a result of the high electron
affinity of a fluorine atom, the interaction is strongly attractive and leads to a considerable polarization of the
𝐻2 charge distribution even at large 𝐹 − 𝐻2 distances.
• As a consequence of the electron’s low inertia, an electron can be transferred to the fluorine atom from the
nearest hydrogen atom, hence forming the HF ionic bond, before the spacing between the hydrogen and
fluorine has adjusted itself to the internuclear separation corresponding to the HF equilibrium distance. This
classical picture indicates that, after reaction has occurred, the HF molecule is left in an excited vibrational
state.
Population Inversion
• As one can see from the above discussion, a consequence of the combined effect of both the cold
and hot reactions, described by Eqs. (10.3.1) and (10.3.2), is that a population inversion between
several vibrational levels of HF is produced in an HF laser.
• If the active medium is placed in a suitable resonator, laser action on a number of transitions from
vibrationally excited HF molecules is thus expected to occur. Laser action has indeed been
observed on several rotational lines of the (ν=1)→ (ν=0) transition up to the (ν=6)→ (ν=5)
transition.
• In fact, due to the anharmonicity of the interaction potential, the vibrational energy levels of Fig.
10.22 are not equally spaced and the laser spectrum actually consists of many roto-vibrational lines
encompassing a rather wide spectral range (λ = 2.7 − 3.3 μ𝑚).
• It should also be noted that the number of observed laser transitions is larger than one would have
expected according to the population inversion situation described in Fig. 10.22.
• There are two reasons why oscillation can occur on so many lines:
(1)The phenomenon of cascading: if, in fact, the (ν=2)→ (ν=1) transition (usually
the strongest one) lases, the population will be depleted from level 2 and will
accumulate in level 1. Consequently, laser action on the (ν=3)→ (ν=2) and
(ν=1)→ (ν=0) transition now become more favored.
(2)The phenomenon of partial inversion, according to which there may be a
population inversion between some rotational lines even when no inversion exists
between the overall populations of the corresponding vibrational levels.
Finally, it should be noted that, besides laser action in HF, laser action can also be
achieved in the analogous compounds DF, HCl, and HBr thus providing oscillation
on a large number of transitions in the 3.5–5 μm range.
Configuration of cw HF Laser
• A possible configuration for a high-power cw HF or DF laser is shown in Fig. 10.23.
• Fluorine is thermally dissociated by an arc jet heater and then expanded to supersonic velocity
through some appropriate expansion nozzles.
• Molecular hydrogen is then mixed downstream through some appropriate perforated tubes inserted
in the nozzles.
• Downstream in the expansion regions, excited HF molecules are produced by the chain reactions
Eqs. (10.3.1) and (10.3.2) and a suitable resonator, with its axis orthogonal to the flow direction, is
placed around this region.
• To handle the large power available in the expanding beam, usually of large diameter, unstable
resonators exploiting metallic water-cooled mirror are often utilized.
• Chemical lasers of this type can produce very large c.w. output powers (in the MW range!) with
good chemical efficiency.
Applications
• Pulsed TEA type HF lasers are commercially available and have found a limited use when an
intense source of middle infrared radiation is needed (e.g., in spectroscopy).
• HF and DF chemical lasers of the type described in Fig. 10.23 are used exclusively for military
applications. Safety considerations have indeed prevented the use of these lasers for commercial
applications.
• In fact, the 𝐹2 molecule is one of the most corrosive and reactive element known, the waste
products are difficult to dispose of, and, under certain conditions, the chain reaction Eqs. (10.3.1)
and (10.3.2) may even become explosive. In the military field, due to the large available output
powers, these lasers can be used as directed energy weapons to e.g., destroy enemy missiles.
• A military c.w. device named MIRACL (Mid-Infrared Advanced Chemical Laser), using DF, has
given the largest c.w. power of any laser (2.2MW). DF rather than HF molecule was used because
the system was intended for use from a ground station and the DF emission wavelengths fall in a
region of relatively good atmospheric transmission.
• More recently, HF lasers of somewhat higher power (5MW) have been constructed. The laser is
intended to be used either from a high altitude plane, for destruction of missile during their ballistic
flight, or from a space station, for missile destruction during their lift-off phase (where the rocket
has much lower speed and hence is much more vulnerable).
Chemical Oxygen Iodine Laser-COIL
• With the success of the HF model, there was intense interest and research in the 1970s to develop
an electronic transition chemical laser that operated at much shorter wavelengths than the HF
system
• COIL was the first electronic transition chemical laser and was initially demonstrated at the Air
Force Weapons Laboratory (now the Air Force Research Laboratory) in 1977.
• The energy for the laser is contained in the 𝑂2 (1∆𝑔 ) and the gain in the 2𝑃1/2 .
• Electronic transition chemical laser via energy transfer from a chemically excited product.
• Chemical production of singlet oxygen
• In fact, megawatt-scale COILs are now tested .
• COIL depends first on the production of 𝑂2 (1∆𝑔 ) in high yield.
• 𝑂2 (1∆𝑔 ) can be produced in many ways
• .
Elaboration
• Even though the chemical process that produced 𝑂2 (1∆𝑔 ) was known, the combination of oxygen and iodine
came in discharge studies.
• They observed that when iodine was added to excited oxygen, a bright yellow glow was seen. This was
recognized as 𝐼2 (𝐵) state emission. They also observed a strong emission at 1.315 μm, the iodine atom
𝟐𝑷𝟏/𝟐→ 𝟐𝑷𝟑/𝟐 transition. The excitation of iodine was attributed to the near-resonant pumping by 𝑶𝟐 (𝟏∆𝒈 ).
• The iodine atoms were thought to be formed by the dissociation of molecular iodine by 𝑂2 (1𝛴𝑔 ). It was
suggested that an inversion could be achieved on the iodine atom 2𝑃1/2→ 2𝑃3/2 transition if a sufficient
fraction of 𝑂2 (1∆𝑔 ) could be produced.
• Using the equilibrium constant for the energy pumping reaction, they showed that a flow containing about
15% 𝑂2 (1∆𝑔 ) could produce an inversion on the iodine 2𝑃1/2→ 2𝑃3/2 transition. This laser uses a process
that is at equilibrium and excites a two-level system terminating in the ground state
• The achievement of lasing in the COIL system depended on two things:
• (1) the production of high amounts of 𝑂2 (1∆𝑔 )
• (2) the ability of 𝑂2 (1∆𝑔 ). to dissociate molecular iodine into iodine atoms.
Major ‘Chemistry’ behind COIL
• Chemistry of Singlet Oxygen production.
• Required Oxygen state generator.
• Iodine dissociation kinetics

Note:
• There are multiple ways to generate the required states for lasing, each having its
own specifications and delicacies.
• The rate of dissociation depends on concentration ratios, mixing dynamics, and
total pressure.
Applications of COIL
• COILs have been proposed for use in material processing, for decommissioning of nuclear reactors, as a laser
fusion driver, and for various defense applications
• As COIL has demonstrated spectrally pure, high-power output with good beam quality, it offers advantages
for several military and commercial applications.
• COIL was selected as the high-power laser for the AirBorne Laser (ABL) system that is developed by the US
Missile Defense Agency. A schematic of the ABL COIL is shown in Figure 9.9.
• The COIL system also has been developed for use in materials processing, such as welding and cutting.
• Japanese researchers have led these efforts and have aggressively developed COIL to mature systems. Figure
9.10 shows a 1 kW COIL welder developed by Kawasaki Heavy Industry.
• Other potential applications include decommissioning and dismantlement of nuclear power reactors and a
laser fusion driver.
• There has also been interest in using a portable COIL for hole drilling for mining applications.
Dye Lasers
• Lasers based on liquid or solid dyes as gain media
• A dye laser is a laser based on a dye (typically in a liquid solution) as
the laser gain medium .
• Most laser dyes are based on organic molecules used in liquid form as
solutions, although solid laser dyes and vapor dyes exist as well.
Dye Lasers
• Dye lasers make use of an active medium consisting of a solution of an organic dye
in a liquid solvent such as ethyl or methyl alcohol, glycerol, or water.
• Organic dyes constitute a large class of polyatomic molecules containing long chains
of conjugated double bonds [e.g. – C ].
• Laser dyes usually belong to one of the following classes:
(1) Polymethine dyes, which provide laser oscillation in the red or near infrared (0.7–
1.5 μm). As an example Fig. 9.12a shows the chemical structure of the dye 3, 3’
diethyl thiatricarbocyanine iodide, which oscillates in the infrared (at a peak
wavelength, λ𝑝 = 810 nm).
(2) Xanthene dyes, whose laser operation is in the visible. As an example Fig. 9.12b
shows the chemical structure of the widely used rhodamine 6G dye (λ𝑝 = 590 nm).
(3) Coumarin dyes, which oscillate in the blue-green region (400–500 nm). As an
example Fig. 9.12c shows the chemical structure of coumarin 2, which oscillates in
the blue (λ𝑝 = 450 nm).
Characteristics
• Typical characteristics of laser dyes as gain media are:
• They exhibit a broad gain bandwidth, which allows for broad wavelength
tunability and also ultrashort pulse generation with passive mode locking.
• A wide range of emission wavelengths from the ultraviolet to the near-
infrared region can be addressed with different laser dyes.
• Intense dye laser pulses can be obtained with pulsed pumping, using a Q-
switched pump laser or a flash lamp.
• The gain per unit length can be fairly high (order of 103 cm−1), particularly
for pulsed pumping.
• The power conversion efficiency is typically between 10% and 30% for
laser pumping, and typically lower for flash lamp pumping.
Variety in dye lasers
• Many different laser dyes are available, and in total they can cover
huge wavelength regions.
• A name like exalite, coumarin, rhodamine, pyrromethene, pyridine,
fluorescein, pyridine or styryl often denotes not a precisely defined
substance, but rather a whole family of dyes with slightly different
chemical structures, having somewhat different ranges of emission
wavelengths and being distinguished with additional numbers.
• For example, one may use coumarin 2, 47, 102 or 153 for lasers in the
blue to green spectral region.
Pumping Options for Dye Lasers

• Dye lasers are normally pumped at relatively short wavelengths. Some typical options
are:
• Many dyes can be pumped with a green laser such as a frequency-doubled solid-state
laser or an argon ion laser. For 532-nm pumping, for example, laser emission may then be
in the green, yellow, orange, red or near infrared spectral region.
• Laser dyes for shorter emission wavelengths (for example, exalite, stilbene and coumarin)
have to be pumped at shorter wavelengths – typically, with ultraviolet light. For example
one may use a Q-switched and frequency-tripled Nd:YAG laser at 355 nm, or
a frequency-quadrupled Nd:YAG laser at 266 nm.
• Other possibilities are to use an excimer laser, a nitrogen laser, or a copper vapor laser.
• Some dye lasers can be pumped with flash lamps. This leads to longer pulses and a lower
power conversion efficiency. However, pulsed pumping with flash lamps allows the
excitation of large volumes and thus the generation of pulses with high energies
(sometimes of the order of 1 J).
Rhodamine dye laser
• Most of the commercially available dye lasers are either Fluorescein or
Rhodamine laser dyes. Rhodamine dyes have efficient fluorescent
characteristics, and can be detected using fluorometers.
• Rhodamine 6G is also used as a laser dye, or gain medium, in dye lasers,
and is pumped by the second (532 nm) harmonic from an Nd:YAG
laser, nitrogen laser, or argon ion laser.
• The dye has a remarkably high photostability, high fluorescence quantum
yield (0.95), low cost, and its lasing range has close proximity to its
absorption maximum (approximately 530 nm).
• The lasing range of the dye is 570 to 660 nm with a maximum at 590 nm
• Rhodamine 700, on the other hand, is another efficient laser dye that
exhibits laser action between 700 and 800 nm in the spectral region.
Applications
• Rhodamines are commonly used in photocoagulation therapy and
ocular photodynamic owing to its large numbers of wavelengths of
high output power.
• Laser lithotripsy using rhodamine 6G dye laser is one of the safest and
effective method that allows fragmentation of complex bile duct stones
under radiological conditions