Laser Uranium Separation

Based on recent discoveries in science and advances
s ince the advent of lasers, these

unique sources of highly intense
and nearly monochromatic radi-
ation have been proposed as tools
to induce or catalyze chemical reactions. Of
all the reactions investigated, laser isotope
separation has received the most attention
in engineering, the LOSAlamos molecular
^. .
worldwide and may be the first major corn-
mercial application of lasers to chemistry.
Laser isotope separation was first demon-
laser isotope separation process appears to be an ^ ^ ago ^ boron and &
date has been applied on a laboratory scale
economical method for uranium enrichment. 10 many elements throughout the ~eriodic
table. But the goal is to find laser processes
that are more economical than conventional
by Reed J. Jensen, O'Dean P. Judd, and J. Allan Sullivan separation techniques. Los Alamos re-
searchers have developed a practical process
for separating sulfur isotopes based on laser
irradiation of sulfur hexafluoride molecules,
and the Soviets have developed comrnercial-
ly applicable laser processes for separating
both sulfur and carbon isotopes.
However, the primary motivation behind
the generous funding of this field is the
LOS ALAMOS SCIENCE

Separating Isotopes WithLasers
promise of an economical method for pro- of uranium235 to that required of reactor thousand chambers are needed to increase
ducing bulk quantities of enriched uranium, fuel, the two isotopes must be sorted accord- the concentration of uranium-235 to the fuel
the fuel of nuclear reactors. Here, success ing to some difference in their chemical or assay of 3.2 per cent required for light-water
has been much harder to achieve. But the physical properties. But the electronic and reactors. Gaseous diffusion thus requires a
difficulties encountered have been beneficial therefore the chemical properties of the two very large and expensive facility and,
in the larger perspective, having stimulated isotopes are so nearly identical that chemical moreover, consumes large amounts of elec-
fundamental scientific advances that are processing is difficult and inefficient. Con- trical energy.
strongly influencing the broad field of laser ventional methods for separating isotopes of
chemistry. Among them are the discovery of Other separation techniques based on
uranium, as well as those of other elements, mass differences include the gas centrifuge,
multiple-photon processes, a revolution in rely instead on physical processes that are
infrared spectroscopy of heavy molecules, an multiple distillation, and electromagnetic sep-
affected by the small differences in the aration. Of these, the gas centrifuge is being
increased understanding of molecular elec- masses of the different isotopes.
tronic structure and of condensation proc- explored as an alternative to gaseous dif-
The gaseous diffusion method, which cur- fusion (see sidebar "Economic Perspective
esses in cooled gases, the development of
new, high-intensity, tunable laser systems, rently produces most of the enriched for Uranium Enrichment").
and practical methods for producing gas uranium for nuclear reactors, consists of What may prove to be more economical is
flows at low temperatures. These advances passing gaseous uranium hexafluoride a separation process driven by lasers. The
have also contributed to major progress in molecules (UFn) through a series of cham- idea is quite simple. Since atoms or
the Laboratory's molecular laser isotope bers separated by porous barriers. The light- molecules containing different isotopes have
separation process for uranium. er molecules, those containing uranium-235, slightly different energy levels, they have
Natural uranium is a mixture of isotopes diffuse through the barriers slightly faster. So slightly different absorption spectra-that is,
and contains 99.3 per cent uranium-238 and in each successive chamber the concentra- they absorb radiation with different frequen-
only 0.7 per cent of the fissile isotope tion of uranium-235 relative to that of cies (Fig. 1). Consequently, radiation of a
uranium-235. To increase the concentration uranium-238 increases slightly. More than a particular frequency can selectively excite an
LOS ALAMOS SCIENCE

P, -^J = -1
Q, -AJ = 0
R , AJ= 1
Rotational
Energy
Levels
Ground State
(a) Wavenumber
Fig. 1. The shift in vibrational energy levels of one molecular shown in more detail. Each vibrational state is split into many
isotopic species relative to another shown in (a) is reflected in rotational states labeled by J, the number of rotational angular
(c) as a shift in the infrared absorption spectra, (a) Within the momentum quanta of the state. At room temperature molecules
ground electronic state of a molecule are many vibrational typically populate rotational states with high J values. During
states resulting from oscillatory motion of the nuclei about a transition between vibrational states, the change in 3, AJ, is
their equilibrium positions. Shown here schematically are the restricted to -1, 0, or +1. Such allowed transitions are
energy levels for a vibrational mode of UF6 known as the v 3 denoted as P-,Q -,and R-branch transitions, respectively. (c)
mode. The energy levels are labeled by v, the number of The infrared absorption bands of 235UF6 and "'UF6 from 620
vibrational energy quanta of the state. The arrows represent to 630 reciprocal centimeters include transitions from the
absorptions of infrared photons that raise a moleculefrom the ground state to the first excited state of the v3 vibrational
ground state to thefirst vibrational state. The different lengths mode. Absorptions that excite the v , mode occur over a broad
of the arrowsfor the two isotopic species represent the different band of frequencies because molecules in the ground state
photon energies, or frequencies, needed to excite the two occupy many rotational states and the molecules in each
isotopic species. The difference, although small (less than 1.25 rotational state can undergo P-, Q-, or R-branch transitions to
x lo'* electron volt, or I reciprocal centimeter, for UF,), the first excited vibrational state. The absorption band of
allows selective excitation by nearly monochromatic laser 235 m6is shifted slightly to higher frequencies relative to that
light. (3) One of the vibrational transitions indicated in (a) is of ""UF~.
LOS ALAMOS SCIENCE

Separating Isotopes With Lasers
atom or molecule containing one isotope to a Alamos and at many other research centers covered only a small number of wavelengths.
higher energy level and leave other isotopic around the world since the early 1970s when M o n o c h r o m a t i c s o u r c e s at other
species undisturbed. Then, depending on the high-intensity tunable lasers became avail- wavelengths were created from conventional
type of excitation, the selectively excited able. However, isotope separation based on white light sources (for example, with filters
species can be separated from the others by selective photoexcitation of atoms and or gratings), but their intensity was even
conventional physical or chemical methods. molecules is not a new idea. In fact, lower.
For selective excitation to be practical as a photochemical separation was attempted High-intensity tunable lasers have re-
separation technique, it must produce a large with conventional radiation sources long moved many of the limitations of the early
change in some chemical or physical proper- before the invention of lasers. In 1922 efforts experiments. Lasers can be tuned to match
ty of the excited species. One possibility is to were made to separate the two naturally any absorption feature that shows a distinct
excite a molecule to such a high energy level occurring chlorine isotopes by irradiating isotope shift. In particular, high-intensity
that its chemical reactivity increases substan- them with white light that had been filtered infrared lasers can selectively excite the
tially. The molecule can then react with through a cell containing only the more isotopically distinct vibrational levels of
another chemical species, and the product abundant chlorine isotope. These experi- m o l e c u l e s . B e c a u s e o f i t s high
containing the desired isotope can be sepa- ments were unsuccessful. About ten years monochromaticity, laser light can excite a
rated from the mixture by conventional tech- later Stanislaw Mrozowski suggested that desired species with reasonable selectivity
niques. This type of bimolecular process has mercury isotopes might be separated by even when absorption features of other
many applications in selective photochemis- selective excitation with the 2 53.7-nanometer isotopic species partially overlap those of the
try. resonance line of a mercury arc lamp and desired isotopic species. Thus, both the
However, the more widely studied laser subsequent reaction with oxygen. This sepa- tunability and high monochromaticity of the
isotope separation techniques involve only ration was achieved experimentally by Kurt laser are crucial for selective excitation.
photons and a single atomic or molecular Zuber in 1935. In the early '40s Harold Urey Other properties of laser light contribute
species. For example, the atomic vapor proc- proposed a photochemical method for sepa- to the efficiency of selective excitation. First,
ess under development at Lawrence Liver- rating uranium isotopes, but his proposal lost since laser light has a high degree of spatial
more National Laboratory uses selective in competition with the gaseous diffusion and temporal coherence, a laser beam can
photoionization to separate uranium technique. After the war, an enlarged effort propagate over long distances and interact
isotopes. Through a multistep excitation t o s e p a r a t e mercury isotopes by efficiently with large volumes of process
process laser photons selectively ionize at- photochemical techniques succeeded in pro- material. Second, a high-intensity laser beam
oms of uranium-235. The ions are then ducing small amounts of product. Carbon can saturate the absorbing material. In other
separated from the neutral uranium-238 at- and oxygen isotopes were also separated by words, the beam contains so many photons
oms by an electric field. using a strong spectral line of an iodine lamp that almost all the molecules that can be
The separation technique being studied at to excite carbon monoxide molecules. excited will be excited. Finally, the laser
Los Alamos uses selective photodissociation These pre-laser experiments involved a pulses are short compared with the average
of molecules into stable fragments. As dis- one-step process in which absorbed photons time for the selectively excited molecules to
cussed below in more detail, a molecule can with frequencies in the visible or ultraviolet lose their energy either through collisions
be excited to the point of dissociation in spectral region selectively excite electronic with unexcited molecules or through other
several ways. A two-step process is the basis states of one isotopic species. Although this loss channels. Short pulses are essential if the
of our technique. An infrared laser selective- technique works in a few isolated cases, it is excitation process is to be isotopically selec-
ly excites vibrations of gaseous UF6 not generally applicable in molecules. Most tive and efficient in its use of laser photons.
molecules containing uranium-235 ("ûF~). molecules have very broad, structureless Laser photons are quite expensive and
These vibrationally excited molecules are electronic absorption bands, and selective represent the major cost in any laser
then dissociated by an ultraviolet laser into excitation is not possible. chemistry process, including laser isotope
uranium pentafluoride ("'uF,) plus a These early efforts were also limited by separation. To illustrate, a mole (6 x of
fluorine atom. The "'uF. molecules the radiation sources then available. photons costs about 1 to 3 dollars, whereas
coalesce to form particulates that are easily Photochemical isotope separation requires chemical reagents typically cost about 10 to
separated from the remaining gas. highly monochromatic, highly intense radi- 20 cents per mole. Efficient use of laser
The various techniques for isotope separa- ation. The few reasonably monochromatic photons is therefore a primary factor de-
tion have been investigated vigorously at Los discharge lamps were not very intense and termining the economy of a laser isotope
continued on page 8
LOS ALAMOS SCIENCE 5

SIDEBAR 1:
6 LOS ALAMOS SCIENCE

They have, however, proved very reliable. smaller, including only about ten separation
The main disadvantage of the process is the units. In addition, the process would con-
great amount of electric power required to sume an equal or lesser amount of energy
operate the many compressors. A standard per SWU than the gas centrifuge. These
gaseous diffusion plant operating at full advantages lead directly to reduced capital
capacity demands about 3000 megawatts and operating costs.
electric. For comparison, a typical large For a laser isotope separation process
electric power plant produces 1000 mega- involving selective excitation of ÛP,;
watts electric. As the cost of electric power molecules with infrared lasers and their dis-
increases, its consumption becomes an in- sociation with an ultraviolet laser, a facility
creasingly important factor in the cost of with the standard capacity of 8.75 millions
enriched uranium. (In fiscal year 1980 about SWU per year is estimated to cost about 1
75 per cent of the production costs at billion dollars. (Laser costs account for ap-
gaseous diffusion plants was for electricity.) proximately half of the direct capital costs.)
With the expectation of reducing power This is considerably lower than the estimated
consumption, attention is now focused on cost of a new gaseous diffusion plant (about
the gas centrifuge, another method for en- 5 billion dollars) or that of a gas centrifuge
riching uranium. The Gas Centrifuge Enrich- plant (about 6 billion dollars). The annual
ment Plant now being constructed at operating cost for a laser isotope separation
Portsmouth, Ohio will contribute 8.75 mil- facility is estimated to be about 100 million
lion SWU per year to the national enrich- dollars, in contrast to about 500 million for a
ment capacity by 1994. In a gas centrifuge gaseous diffusion plant and 100 to 200
2 3 5 ~ ~and
6 ^ U F ~ are separated by the million for a gas centrifuge plant. Our esti-
centrifugal force imposed on UPo by a mates of capital and operating costs for a
rapidly rotating container. For this process a laser isotope separation facility indicate a
considerably smaller number of centrifuge cost per SWU of about $30; the current
units (less than 10) are required to reach the commercial cost for enriched uranium is
desired enrichment. However, the through- $1 10 per SWU.
put per centrifuge unit is very small com- The considerably lower cost per SWU for
pared to that of a diffusion unit-so small, in laser isotope separation opens the possibility
fact, that it is not compensated by the higher of turning the large stockpile of wastes from
enrichment per unit. To produce the same gaseous diffusion plants into a valuable
amount of reactor-grade fuel requires a con- uranium resource. These wastes contain
siderably larger number (approximately about a third of the ûF.,originally present
50,000 to 500,000) of centrifuge units than in the feed material and are estimated to
diffusion units. This disadvantage, however, amount to more than 500,000 metric tons by
is outweighed by the considerably lower (by the end of 1990-an amount containing
a factor of 20) energy consumption per enough uranium-235 for 1800 reactor-years
SWU for the gas centrifuge. of operation.
Compared to diffusion and the centrifuge, These advantages imply that laser isotope
laser isotope separation offers the potential separation should be thoroughly investigated
for much greater enrichment and throughput as a potentially economical process for
per separation unit. Therefore, a laser large-scale production of enriched
isotope separation facility would be much uranium.

cut~nuedfrom page 5
separation process.
We said earlier that a fairly large amount
of energy must be deposited in a molecule to
make a substantial change in its physical or
chemical properties. In the pre-laser experi-
ments this energy was deposited through a
one-step, or single-photon, process. When
high-intensity infrared lasers became avail-
able, new multistep excitation processes be-
came possible. Unlike the single-photon
process, these multistep methods can achieve
isotopic selectivity on virtually all atoms or
molecules.
In the sections that follow, we will de-
scribe these excitation methods and their
application to isotopes of medium and heavy
elements. Great success has been achieved in
separating medium-weight isotopes with in-
frared photons through what is known as
multiple-photon excitation and dissociation.
Progress has also been made on the more
difficult problem of separating isotopes of
heavy elements such as uranium. Labora-
tory-scale experiments based on the in-
frared-plus-ultraviolet dissociation of UF6
have been very successful. The lasers and
gas flow systems necessary to scale up the
process have been built, and designs for a
full-scale plant have been studied. But
challenges still remain in both the science
and engineering needed to optimize the proc-
ess and its economics on a large scale. The
physics of the molecular excitation is not
sufficiently d e f i e d to choose process param-
eters that optimize selectivity, and some
problems associated with irradiating large
volumes of material have yet to be solved.
But we are rapidly drawing nearer to our
goal. Fig. 2. In the ground-state configuration the fluorine nuclei in a surur hexafluoride
(SF& molecule occupy the vertices of a regular octahedron about the central sulfur
Molecular Laser Isotope nucleus. Shown here are the six fundamental vibrational modes that, singly or in
combination, describe the complex motion of and other octahedral molecules,
Separation Methods
such as UF6. m y the v3 and v4 modes can be excited by absorption of infrared
photons, and, since only these modes involve motion of the sulfur nucleus, any shifts
Three methods of molecular photodissoci- due to suffur isotopes are confined to these particular modes. The v3 mode stretches
ation have been used successfully to separate one S-F bond and compresses a second S - F bond that is colinear with thefirst. The v4
isotopes: a single-photon process, in which a mode bends the four coplanar S-F bonds.
LOS ALAMOS SCIENCE

\ \ Excited-State Potential Curve

Consequently, vibrational excitation of a
molecule containing a lighter isotope requires
absorption of a photon at a higher frequen-
cy. This mass-dependent shift in the absorp-
tion spectrum has been exploited to dis-
sociate molecules of one isotopic species
- - - ^V\/\/\/\-Ã Dissociated Molecule selectively and thus achieve isotope separa-
tion.
PREDISSOCIATION. The usual photo-

dissociation process involves a photon-
' Laser Induced
Transition
induced transition from a bound ground
electronic state to an electronic state for
Dissociation
which the internuclear forces are always
repulsive. The lifetime of such a repulsive
Ground-State Potential
electronic state is so short that dissociation
Curve follows the transition with nearly unity prob-
w Isotopically Distinct Vibrational Levels
Internuclear Distance
ability. Predissociation (Fig. 3) involves a
photon-induced transition not directly to a
repulsive electronic state but to a pre-
dissociative state-a vibrational state within
a bound excited electronic state that is
energetically coupled to the repulsive elec-
tronic state. That is, the bound excited and
repulsive electronic states have the same
energy (the curve-crossing energy) at some
Fig. 3. Predissociution. The three potential energy curves depict the molecular binding internuclear distance greater than the
energy as a function of internuclear distance. The curves for the ground electronic equilibrium internuclear distance for the
state and the bound excited electronic state exhibit energy minima and thus represent ground electronic state. Then, if the bound
stable molecular configurations. The curvefor the repulsive electronic state represents excited and repulsive electronic states have
an unstable configuration in which the molecule dissociates because the forces are certain symmetry relations and if the energy
always repulsive. The usual photodissociation process involves a transition directly to of the vibrational state is near the
a repulsive electronic state. The arrow represents a photon-induced transit ion of one curve-crossing energy, dissociation occurs
isotopic species to a vibrational state within the bound excited electronic state. This by tunneling from the bound excited elec-
transition can result in predissociation in which the molecule tunnelsfrom the bound tronic state to the repulsive electronic state.
This dissociation by tunneling is called pre-
excited electronic state to the repulsive electronic state and then dissociates.
dissociation because it requires a photon
energy less than that required for dissocia-
visible or an ultraviolet photon excites a In all these processes, including pre- tion directly from the repulsive electronic
molecule to a "predissociative" state; a dissociation, selectivity is based on the state. By tuning a laser to the frequency
two-step process, in which an infrared isotopically distinct energies of the matching the transition energy of the
photon excites a vibrational state of a molecule's vibrational states. In a vibrational isotopic species of interest, that species can
molecule and an ultraviolet photon dis- state the nuclei of a molecule undergo be selectively excited and dissociated.
sociates the excited molecule; and a multi- oscillatory motion about the ground-state A requirement for isotopic selectivity of
step infrared process, in which infrared configuration (Fig. 2) at some frequency. predissociation is that the shift of the vibra-
photons excite successively higher and high- This frequency depends on the masses of the tional energy levels for the different isotopic
er vibrational states of a molecule until its nuclei. In particular, molecules containing species be greater than their energy widths.
dissociation limit is reached. lighter isotopes vibrate at higher frequencies. The energy width of a state is determined in

part by its lifetime, and longer-lived states
h a v e narrower energy widths. Pre-
dissociative states in some molecules are
relatively long-lived, and selective pre-
dissociation not only works but also has a
high quantum yield. That is, if the molecule
absorbs a photon of the right frequency to
raise it to a predissociative state, it will
almost always dissociate rather than decay
to lower-energy states through emission of
photons.
One successful application of this process
is the predissociation of formaldehyde
Dissociation
(HiCO) to produce carbon monoxide en- Dissociation Limit
riched in carbon-13. Laser photons with a 'with Ultraviolet
wavelength of 334 nanometers excite Laser
H ~ ^ C Omolecules to a vibrational level of an
excited electronic state that predissociates
into hydrogen and carbon monoxide
molecules. Some of the H ~ ^ C Omolecules
also dissociate, but early experiments pro-
duced carbon monoxide with a concentra-
=$ Isotopically Distinct
vibrational Energy Levels
tion of carbon- 13 greater by a factor of 3 or Selective Vibrational Excitation

4 than its initial natural isotopic abundance. with Infrared Laser
Predissociation of formaldehyde with a
laser of different wavelength has also been
Internuclear Distance
studied as a practical way to separate hydro-
gen and deuterium. From an equal mixture
of H 2 C 0 and DiCO, products have been
obtained with deuterium-to-hydrogen ratios Fig. 4 . In two-step photodissociat ion, an infrared laser selectively excites a vibrational
of 9, in contrast to the original ratio of 1. level of one isotopic species and thereby raises molecules of that species closer to the
Although these results seem impressive, the
dissociation limit. An ultraviolet laser then raises the excited molecules to an unstable
natural abundance of deuterium is so small
(about 0.015 per cent) that the enrichment electronic configuration represented by the repulsive potential. The molecule then
must be increased significantly for any prac- dissociates into stable chemical fragments. (Predissociation can also occur in the
tical application. ultraviolet step.)
This process is being actively investigated
by the Canadians at Ontario Hydro for
production of the heavy water needed in 1000, and experiments based on mul- quantum yield for this process is quite high,
their CANDU (Canadian deuterium uranium) tiple-photon dissociation have also demon- but selectivity is limited to a few molecules
power reactors. A CANDU reactor requires strated high enrichments. These results in- with distinct features in their electronic
about 800 kilograms of heavy water per dicate that laser isotope separation may be a absorption spectra. However, we can make
megawatt of capacity, and at the present potentially promising technology for photodissociation selective in a very wide
cost of $250 per kilogram, the heavy-water low-cost production of heavy water. range of molecules by breaking the process
inventory represents about 15 to 20 per cent into two steps, the first providing high selec-
of the total capital cost of the reactor. Recent TWO-STEP PHOTODISSOCIATION, In pre- tivity and the second efficient dissociation
predissociation experiments at Ontario dissociation a single laser provides both the (Fig. 4).
Hydro show enrichments on the order of isotopic selectivity and the dissociation. The In the first step infrared lasers selectively
LOS ALAMOS SCIENCE

quires an ultraviolet photon with an energy,

and hence frequency, lower than that re-
quired for dissociation from the ground state.
In an ideal situation the lower-frequency
ultraviolet photons will not dissociate the
unexcited molecules, and the selectivity of
the first step will be preserved.
In this two-step process the excitation and
the dissociation must occur on a time scale
Vibrationally that is short compared to the lifetime of the
Excited intermediate vibrational state. Otherwise, the
Molecules excited molecules can lose their vibrational
energy through collisions to other isotopic
species or to lower-energy vibrational states
not accessible to dissociation. Since the CO,
laser is normally operated with a pulse length
of 50 to 100 nanoseconds, which is shorter
than the lifetime of the vibrational state,
most vibrationally excited molecules will not
lose their energy before being dissociated by
the ultraviolet laser pulse if the pressure of
the absorbing molecular gas is sufficiently
low. For 100-nanosecond pulses the gas
pressure must be a few torr or less to avoid
the effects of collisions.
Two-step photodissociation has been ap-
plied successfully to the separation of carbon
isotopes in trifluoroiodomethane (CF31).
This molecule has a strong vibrational
absorption at a frequency covered by the
Fig. 5. The (ffect of vibrational excitation induced by an ifrfrared laser on the
CO-, laser. Among the parameters influenc-
ultraviolet dissociation cross-section spectrum of CFJ. Vibrational excitation in-
ing the dissociation are the frequency of the
creases the dissociation cross section at a given ultraviolet frequency and shifts the ultraviolet laser and the fluence of the in-
spectrum to lowerfrequencies. At about 29,000 c m l the dissociation cross sectionfor frared laser. (The fluence, or time-integrated
the selectively excited molecules is about 10 tunes larger than that for the unexcited intensity, of a laser beam is a measure of its
molecules. Data from "Laser Isotope Separation of Carbon by MultipIe IR Photon energy per unit beam area.)
and Subsequent UV Excitation of CFJ Molecules," I, N. Knyazev, Yu. A. Figure 5 shows the ultraviolet dissociation
Kudriavtzev, N. P. Kuzmina, V. S. Letokhov, and A. A. Sarkisian, Applied Physics 17, cross section, or dissociation probability, as
4 2 7-429 (I 978). a function of ultraviolet photon frequency.
Before infrared excitation the dissociation
cross-section spectra for different isotopic
excite the vibrational states of one isotopic wavelengths centered around 10 micro- species are nearly the same. The cross sec-
species and not the others. To date most meters with a pulsed optical output that can tion is zero at low frequencies and then rises
experiments involving selective vibrational be varied over a wide power range. steeply to a nearly constant value. Infrared
excitation have dealt with molecules whose The second step is dissociation of the excitation increases the photodissociation
vibrational transition frequencies overlap the selectively excited moleucles with an ul- cross section at a given frequency and shifts
output frequencies of the carbon dioxide traviolet laser. Figure 4 shows that dissocia- the threshold for dissociation to lower fre-
(COJ laser. This laser operates at several tion from a vibrationally excited state re- quencies (to the red). This shift allows one to
LOS ALAMOS SCIENCE

choose an ultraviolet laser frequency at
which the dissociation cross section is large
for excited molecules (the selected isotopic
species) and small for unexcited molecules. If
the infrared excitation were perfectly selec-
tive, the ratio of the dissociation cross sec-
tion for the excited molecules to that for the
unexcited molecules at a given ultraviolet
frequency would be a direct measure of the
highest enrichment attainable.
Figure 6 shows that the dissociation cross
section increases with the fluence of the
infrared laser. Therefore, one might expect
better selectivity a t higher fluences. But be-
cause the selectivity of the infrared excitation
is finite, some molecules of the unwanted
isotopic species are vibrationally excited.
Higher infrared fluence increases the dissoci-
ation cross section of these molecules also.
Consequently, higher fluence increases the
concentration of the unwanted isotopic spe-
cies in the product and thus degrades the
overall selectivity. A similar situation holds
in the case of heavy elements.
MULTIPLE-PHOTON DISSOCIATION. Fig-

ure 6 also shows that the threshold frequen-
cy for ultraviolet dissociation shifts more and
more to the red as the infrared laser fluence
increases. These relatively large shifts clearly Fig. 6 . The low-frequency edge of the ultraviolet dissociation cross section spectrum
indicate that the CO, laser is exciting the for CFJ. Each curve is labeled by thefluenee of the infrared laser pulses that provided
molecules to very high vibrational states.
vibrational excitation of the molecules. As the infraredfluence increases, the cross
Thus, many photons of equal energy are
section at a particular ultraviolet frequency increases and the thresholdfrequency for
being absorbed by a single molecule, a very
surprising result! If molecular vibrations dissociation shifts more and more to the red, that is, to lower frequencies. This red
were governed by forces that increased line- shift indicates that higher infraredfluences raise the molecules to higher vibrational
arly with displacement, as they are in a states. Data from source cited in Fig. 5.
harmonic oscillator, the energy difference
between vibrational states would be constant infrared photons of lower energy and its and many triatomic molecules. Experiments
and photons with this constant energy could interaction with constant-energy photons have shown, however, that polyatomic
"resonantly" induce transitions to higher and should quickly become nonresonant and in- molecules can absorb many single-frequency
higher vibrational states (Fig. 7a). But most effective. infrared photons, and these photons can
molecular vibrations are anharmonic, that is, The discussion above suggests that a excite the molecule to high vibrational states
t h e y involve nonlinear forces. T h e molecule should absorb only one photon at and even to the dissociation limit (Fig. 7b).
anharmonicity results in progressively the frequency corresponding to the energy of Even more intriguing is the fact that this
smaller energy differences between vibra- the transition from the ground state to the multiple-photon process can be isotopically
tional states. Thus, as a molecule's vibra- first vibrational state. In fact, this type of selective and can therefore be used for
tional energy increases, it should absorb resonant absorption is observed in diatomic isotope separation.
LOS ALAMOS SCIENCE

are not unique; conceptually different models
can be made to fit the experimental data.
Moreover, collisional effects have not been
modeled nor is their inclusion straight-
forward. Additional work will be required to
provide a satisfactory a n d detailed
understanding of the complex interaction
between the molecules and the radiation Held
(see "Multiple-Photon Excitation" in this
issue). There still exist two basic questions.
How is the absorbed energy distributed
among the various vibrational modes of a
molecule at different degrees of vibrational
excitation? And how does absorption of one
photon affect the absorption probability for
the next?
Despite these uncertainties we know that
multiple-photon excitation plays a key role in
all molecular isotope separation processes
that include vibrational excitation. And the
Fig. 8. The low-intensity v, absorption bands of and "SF6. The absorption band
process provides an efficient means of sepa- for the heavier isotopic species is shifted to the red by 17 c m ' . The Q-branch peaks
rating isotopes in medium-weight molecules correspond to transitions in which J does not change. The P and R branches
using infrared lasers alone. correspond to transitions in which AJ = -1 and + I , respectively (see Fig. 1).
The three photodissociation techniques
described above can be used t o separate can be detected by nuclear magnetic reso- which J, the quantum number for the
isotopes of most elements. Table I lists some nance techniques. Its applications include molecule's rotational angular momentum,
of the elements whose isotopes have been agricultural studies and structural studies of does not change. The other portions of the v3
separated a t Los Alamos. This list could be proteins. absorption band, called P and R branches,
extended substantially by including pub- The Los Alamos process for separating correspond to v3 transitions in which 3
lished results from other research institu- sulfur isotopes is based on SF6, an oc- decreases and increases, respectively, by
tions. tahedrally symmetric molecule like UF6. unity. Note the 17-reciprocal centimeter
Some researchers refer to SF6 as the hydro- c m ) isotope shift of the Q-branch peak
gen atom of multiple-photon excitation be- from 931 cm-1 for "SF. to 948 cm-I for
Laser Isotope Separation in SF6 cause it is the molecule most studied in the 32s~6.
attempts to understand the phenomenon. In early investigations of SF6, we could
Here we will discuss only those results not even resolve the smaller peaks near the
A more detailed look a t the work done on relevant t o isotope separation. Q-branch peaks nor could we identify the
separating sulfur isotopes will illustrate spe- Portions of the low-intensity infrared specific transitions that give rise to the
cific features of selective multiple-photon absorption spectra of "SF^ and SF^ a t Q-branch peaks. Thanks to the revolution
excitation, as well as generic considerations room temperature are shown in Fig. 8. that has occurred over the past seven years
involved in the development of a practical Absorption at these frequencies induces ex- in high-resolution molecular spectroscopy,
molecular isotope separation process. citation of the v3 vibrational mode of the we now know what transitions are being
The four naturally occurring isotopes of molecule's ground electronic state (see Fig. excited in the Q branch as well as the origin
sulfur and their abundances are sulfur-32 2). There are many absorbing transitions of the subsidiary peaks. Called hot bands,
(95.0 per cent), sulfur-33 (0.76 per cent), corresponding to different initial and final the subsidiary peaks are due to v3 vibrational
sulfur-34 (4.22 per cent), and sulfur-36 (0.02 rotational states of the v3 vibrational mode. transitions from low-energy vibrational
per cent). The odd-nucleon isotope sulfur-33 The highest peak for each isotope, labeled Q states rather than the molecule's ground
is of value as a tracer because its presence in Fig. 8, results primarily from transitions in state (see "The Modern Revolution in In-
LOS ALAMOS SCIENCE

~ Separating Isotopes With Lasers
frared Spectroscopy" in this issue). This tion of SF6 as a function of laser fluence at a laser intensity is superimposed on the
detailed spectroscopic data has provided the laser frequency of 944 c m . We see that at low-intensity absorption spectrum. Why this
basis for quantitative theoretical models of low fluences only the "SF,, molecules are laser tuning is optimum for SF^ seems
the excitation process. dissociated, but at higher fluences the other puzzling until we realize that the laser is
Pulses from a CO, laser tuned near either isotopic species may also dissociate. This pumping molecules up the entire ladder of
of the isotopically distinct Q-branch peaks of decrease in selectivity is predominantly due vibrational states, all the way to dissociation.
the v3 vibrational mode of SF6will selectively to a broadening of the vibrational states' Since the energy difference between vibra-
dissociate that isotopic species if the laser energy widths in the presence of intense tional states decreases as the molecules reach
intensity is sufficiently great. The dissociated radiation fields. higher states, those molecules some distance
molecules, namely SF., then undergo further At high laser intensity we can achieve the up the ladder will more readily absorb radi-
dissociation to SF4, which is then converted best selectivity for SF^ by tuning the laser ation at frequencies lower than the frequency
to SOF, for separation from the other to the red of its 948-cm' peak in the required to reach the first vibrational state.
chemical species by fractional distillation. low-intensity spectrum, or closer to the ex- Thus, the frequency for selective vibrational
The selectivity of this process depends on citation frequency of the unwanted isotopic excitation at high intensity is red-shifted
both the laser frequency and its fluence. species. We can see this quantitatively in Fig. from that at low intensity.
Figure 9 shows the probability for dissocia- 10, where the dissociation spectrum at high One measure of the efficiency of an
LOS ALAMOS SCIENCE

Fig. 9. Probability of dissociation for and "SF. as a function of C 0 2 laser
fluence. The laser is tuned to 944 c m l , slightly to the red of the Q-branch peak of
"SF,, and far to the blue of the Q-branch peak of ^'SF. (see Fig. 8). The dissociation
probability increases sharply with laserjluence. At lowjluences only dissociates,
but at high fluences ^SF. also dissociates. With the laser tuned to 944 c m l , the best
compromise between selectivity and the amount of " s F 4 produced is achieved with
fluences in the range o f 2 to 8 ~ / c mData
~ . from "Energy and Pressure Dependence of
the C 0 2 Laser Induced Dissociation of Suffur Hexafluoride," W. Fuss and T. P.
Cotter, Applied Physics 12,265-276 (1977).
Fig. 10. Comparison of the high-intensity multiple-photon dissociation probability

spectra (dashed) and the low-intensity absorption spectra for SF^ and 3 2 S ~shows 6
that the best selectivity for multiple-photon dissociation of "SF. occurs with the
high-intensity laser tuned to the red of its low-intensity absorption peak. This red shift
is caused by the anharmonicity of the molecule's vibrational energy ladder. Dissocia-
tion probability data from "Explanation of the selective dissociation of the SF6
molecule in a strong IR laser field," R. V. Ambartsumyan, Yu. A. Gorokhov, V. S.
Letokhov, G. N. Makarov, and A. A. Puretskii, JETP Letters 23, 22 (1976).
LOS ALAMOS SCIENCE

Fig. 11. Photograph of plant prototype constructed at Los area leading into the photolysis chamber (centerfront) and the
Alarnos for production of suJfur-33 and sulfur-34 by multi- high-repetition-ratepulsed C 0 2 laser (center rear).
pie-photon dissociation of S&. Shown are the gas expansion
isotope separation process is the enrichment To see how well the process would work peak, selectively dissociates the molecules by
parameter p. In the case of the sulfur on a larger scale, Los Alamos scientists have multiple-photon excitation and produces
isotopes, p for, say, sulfur-34 is defined a s constructed and operated a small plant pro- ' 3 plus~ fluorine
~ atoms. Back reaction of
totype for production of sulfur-33 and sul- the fluorine atoms with SF^ is prevented by
fur-34 by multiple-photon dissociation. The adding hydrogen and a small amount of
prototype (Fig. 11) consists of a gas re- water vapor to the system. A fast chemical
circulation system that provides a con- reaction occurs that converts SF4 to SOF2,
tinuous flow of SF6 gas through an irradia- which is chemically inert and can be sepa-
where ^N and "N are the number densities tion zone and a C 0 2 laser with an output rated from the other chemical species.
of sulfur-34 and sulfur-32, respectively. The energy of 0.5 joule per pulse that irradiates After a fixed period of operation, the gas
laboratory experiments based on multiple- the gas at a repetition rate of 200 hertz. is pumped from the system, and the various
photon dissociation of SF6 with sin- Dimensions of the irradiation zone in cen- chemical species are separated in a distilla-
gle-frequency infrared radiation have pro- timeters are 50 by 0.3 by 0.3. The laser, tion column. In 6 hours this system produces
duced values of p^ as high as 1000. tuned to the SF^ high-intensity absorption about 1 gram of SFg with a pS4of about 2.2
LOS ALAMOS SCIENCE

The first step in this process, selective

excitation by infrared lasers, is the most
critical and has been much more difficult to
achieve in UF6 than in SFg. The reasons are
twofold. First, although the CO, laser con-
veniently covered the 10-micrometer region
corresponding to the frequencies of the SFi
v3 vibrational mode, no lasers were available
at the frequencies of the UF6 vibrational
transitions. The strongest absorption in UF6
corresponds to v3 transitions around 16
micrometers; consequently, we had to design
new high-intensity pulsed lasers at these
frequencies. Our success represented a
first-usually a laser is developed before its
applications are known. However, develop-
ment of the appropriate laser systems at the
Fig. 13. At room temperature only a very small fraction (about four-thousandths) of required frequency and intensity specifica-
the molecules in a sample of & at room temperature occupies the ground state. Most tions took some time and was a pacing item
of the molecules are distributed as shown here among many vibrational states. (The during the early years of the program (see
sidebar "Lasers for Uranium Enrichment").
lowest vibrational state is at 143 c m l and the lowest state of the v3 vibrational mode The second set of problems arises from
is at 628 e m ' . At 300 kelvin the thermal energy is 210 ern1.) Therefore, at room the fact that uranium is a heavy element,
temperature only a smallfiaction of the molecular population can be excited with a much heavier than sulfur. The isotope shift
narrow bandwidth laser. of the v3 vibrational mode of UF6 is less than
1 c m l compared to 17 c m l for SF6. The
demonstrated for osmium by Soviet re- nornical process for enriching uranium. Our power broadening mentioned in the previous
searchers. They separated osmium- 187 (1 -6 early decision to focus on a molecular rather section therefore becomes much more seri-
per cent) and osmium- 192 (4 1 per cent) by than an atomic process was based in part on ous. Moreover, because the fundamental
selective dissociation of osmium tetroxide the fact that a molecular process offered vibration modes of UF6 are much lower in
(Os04) with a pulsed CO, laser. The isotope more possibilities. For several reasons the energy than those of SF6, at room tem-
shift in the absorption spectrum of this molecule selected was UF6. One reason was perature most of the UF6 molecules are not
molecule is 1.3 c m . Single-frequency ex- that the techniques for handling this gas were in the ground vibrational state but are dis-
citation produced a P I g 7 of only 1.15. With well known from its use in gaseous diffusion tributed among thousands of vibrational
two-frequency excitation Pig7 was increased plants. We chose a two-step (in- states (Fig. 13). Even high-energy vibrational
to 1.5. Since the fractional increase of the frared-plus-ultraviolet) photodissociation states of UFt (those with energies much
enriched product varies as (3 - 1, the process, several years before the discovery of greater than thermal energy) are populated
two-frequency excitation increased this multiple-photon dissociation. at room temperature because of their large
quantity by a factor of 3. The idea was to selectively excite the v, degeneracies. Hence only a small fraction of
vibrational mode of ûF,, (analogous to the the molecular population can be accessed
v3 mode of SF6 shown in Fig. 2) and then with a narrow bandwidth laser. In addition,
The Uranium Enrichment Process dissociate the excited molecules with an the v3 absorption band of UF6 is significantly
ultraviolet laser into fluorine atoms and broadened and red-shifted at room tem-
The primary motivation behind laser ^ U F ~ . The UF5 molecules condense into perature, and any spectral features with an
isotope separation studies at Los Alamos has particulates that are easily separated from isotope shift are obscured within the
been the development of an efficient, eco- the process material. room-temperature bandwidth of about 30
continued on page 22

SIDEBAR 2:
ation) has achieved the status of a familiar "pumped" to achieve a population inversion. Electron
word. But the principles upon which lasers bombardment or exposure to an intense light source are
operate may not be so familiar. Atoms or molecules can common methods of pumping. And usually the active
exist only in certain definite energy levels. In the presence medium must be contained within a suitable optical
of a photon with an energy equal to the difference cavity, such as a pair of highly reflecting mirrors. The
between the energies of two such levels, atoms or cavity provides the feedback for lasing. T o extract energy
molecules can undergo either of two processes, absorp- from the cavity, one of the mirrors is partially trans-
tion or stimulated emission. In absorption, the more mitting. The output of the cavity is an intense, highly
familiar process, an atom or molecule in the lower energy monochromatic beam of light.
level absorbs the photon and makes a transition to the Compared to light from other sources, laser light can
upper energy level. In stimulated emission an atom or be much more intense, monochromatic, and directional.
molecule in the upper level makes a transition to the lower Lasers producing such light with wavelengths ranging
level and emits a photon. The emitted photon and the from the ultraviolet to the far infrared are now available.
stimulating photon are spatially and temporally coherent In fact, some lasers can be tuned to cover a wide range of
(that is, they have the same phase and energy) and travel wavelengths. The many applications of laser light take
in the same direction. If the upper energy level has a advantage of one or more of its unusual properties.
greater population of atoms or molecules than the lower Normally, a laser is developed before its applications
level (a condition known as population inversion), an are conceived. But our program for enriching uranium
intense field of coherent radiation can be produced as the presented the reverse situation-the application was a t
emitted photon in turn stimulates another atom or hand, but lasers with the required properties did not exist.
molecule in the upper level to emit a photon, and so on. The properties demanded of an infrared laser for the
The atoms or molecules are then said t o be lasing. first step in our enrichment scheme, selective vibrational
Developing a working laser is not as simple as explain- excitation of ÛF6 molecules, were a wavelength near 16
ing its operating principle. The first requirement is a micrometers, narrow frequency bandwidth, high energy
collection of atoms or molecules among whose energy per pulse (greater than 0.1 joule), and short pulse length
levels are suitable upper and lower levels between which (on the order of 0.1 microsecond). Another highly
lasing can occur. (Suitable here refers to the ease of desirable, if not mandatory, property was tunability.
producing and maintaining a population inversion. That either continuous or in discrete steps. Our search for such
is, the upper level must be easily populated, and the lower a laser began about eight years ago with suggestions from

I Separating Isotopes With Lasers

c m l . The only way to increase the
ground-state population and narrow the
absorption features is to cool the gas.
Figure 14 shows the collapse of the UF6
population into the ground state and a few
low-energy vibrational states as the tem-
perature is decreased. This collapse sim-
plifies the v3 absorption band, as shown in
Fig. 15. At room temperature and relatively
high density the band has very broad fea-
tures that obscure the Q-branch peaks of
both isotopes. But at low temperature a
medium-resolution spectrum shows sharp,
well-separated Q-branch peaks for the two Fig. 14. Calculated thermal populations in the ten lowest vibrational levels of UF6as a
isotopic species. function of temperature. As the temperature decreases, a greater fraction of the
More detailed low-temperature spectra
molecules occupies the ground state and the lower vibrational levels. This situation
have been obtained by scanning across the v,
leads to greater selectivity of vibrational excitation and access to a larger UF6
absorption band with a tunable serni-
conductor diode laser. A significant effort
population.
has gone into determining the exact value of
the isotope shift and identifying the specific
rotational-vibrational transitions that can be
excited in this frequency interval. Figure 16
shows a high-resolution scan near the "'UK
Q-branch peak. In the Los Alamos uranium
enrichment process the infrared laser is
tuned to a frequency in this region. A
spectrum at even higher resolution would
show many additional rotational subcompo-
nents within the structure of Fig. 16. As
discussed in "The Modern Revolution in
Infrared Spectroscopy," these subcompo-
nents are due to Coriolis forces and oc-
tahedrally invariant tensor forces. The
choice of a particular frequency for the
selective infrared excitation is based on this
detailed knowledge of the low-intensity
absorption spectrum.
EXPANSION SUPERCOOLING OF UF6.

Fig. 15. The v3 absorption band of expansion-cooled natural-assay UF6 exhibits
Knowing that any uranium enrichment proc- narrow, distinct Q-branch peaks for 238UF6and In contrast, the
ess would require cooling the UF6 gas to low room-temperature band is broad and the isotopicfeatures are merged. (For clarity the
temperature before infrared excitation, we 2 3 5 ~ 6 p e isa increased
k in height. The Q-branchpeak heightsfor a sample containing
sought a n efficient and practical means of the natural mixture of uranium isotopes are in the ratio of about 140 to I.)
LOS ALAMOS SCIENCE

The major question concerning this cool-

ing method was whether the gas emerging
from the nozzle would remain in the gas
Fig. 16. A small portion of the v3 absorption band of UF6at high resolution. This scan
phase long enough for the lasers to act on
of a sample enriched to 3 per cent in uranium-235 was obtained with a tunable
single molecules. After expansion the gas is
semiconductor diode laser. The sharp peaks labeled 238 CF6 result from R-branch in a nonequilibrium state of supersaturation
transitions in UF6. and has a strong tendency t o condense
within the flow. At a given temperature the
major factor controlling condensation is the
UF6 number density in the flow-cooled re-
gion. The theory of homogeneous condensa-
tion was not well developed at the start of the
project. We have since developed detailed
theories and performed extensive experi-
ments o n condensation showing that ex-
pansion supercooling is a suitable technique.
Measurements indicate that the nozzle pro-
duces uniform supersonic flow in the central
core with only small turbulent-flow bound-
aries near each wall of the flow channel.
The ratio of final to initial temperature
during supersonic expansion is equal to
(P/PJ*'-I)'*', where P and Poare the final and
initial pressures and y is CnICy , the ratio of
specific heats at constant pressure and cons-
tant volume. When y is very nearly unity, as
it is for a gas of large polyatomic molecules
such as UF6, the initial pressure and/or the
nozzle area expansion ratios must be very
large to achieve substantial cooling. T o cir-
cumvent this constraint, small amounts of
UF6 are mixed with a carrier gas consisting
Fig. 17. Photograph of puked recirculating loop. This compact system provides a high of atoms or small molecules (for example,
density of supercooled UFi, monomers for spectroscopic measurements and enrich- argon or nitrogen) with a larger y. Under
ments experiments. The system is simple and operates routinelyfor several hours. these conditions substantial gas cooling can
be achieved with only modest initial pressure
and nozzle area expansion ratios. The carrier
cooling. Static cooling was impossible be- supercooling, a cooling method that was gas also provides a collisional environment
cause the very low vapor pressure of solid subsequently used not only in the isotope that ensures continuum fluid flow and
UF6 would provide too few molecules in the separation experiments but also in the high- thermal equilibrium among the vibrational,
gas phase, and it is these molecules on which resolution spectroscopy experiments. (Ex- rotational, and translational degrees of free-
the laser process is designed to work. Early pansion supercooling has since become stan- dom of the UFi before irradiation.
in the program Theodore Cotter suggested dard practice in high-resolution spec- The first infrared absorption measure-
the use of a supersonic nozzle for expansion troscopy.) ments on UF6 at low temperature were
LOS ALAMOS SCIENCE

. - Monomer Mixture at Low Temperature
2. Resonant Infrared Excitation of 2 3 5 ~ ~ 6
accomplished in a blowdown mode in which

the supersonic gas flow from the nozzle was
Excitation
dumped into a large (150 cubic meter) of i 3 Mode
evacuated tank. The duration of continuous
supersonic flow, which was set by the vol-
ume of the dump tank, was about 20 sec- <R Laser at thr v3 Fundamental
onds. The time between runs was 2 hours. Frequency of 2 3 5 ~ ~ 6
Despite the slow turnaround time, this setup

provided many of the early data on shifts
and simplifications in the UF6 spectrum at 3. Multiple Photon Excitation of Excited Molecules
low temperature.
Experiments a r e now done in a Further
Vibrational
closed-cycle system known as a pulsed re- Excitation
circulating loop (Fig. 17). Since the lasers
used in the experiments are pulsed at low
repetition rates, a continuous gas flow and a
large compressor train to move the gas
through the system were unnecessary. T o
produce a pulsed gas flow coincident with
4 Dissociation
the laser pulse, the recirculating loop in-
^
cludes a fast-acting hydraulic valve at the
entrance to the nozzle. The valve is actuated Dissociation
to U F 5 + F
at a typical rate of 1 hertz and provides a
fully supersonic flow of cooled gas lasting
about 2 milliseconds at the nozzle exit. With
this system experiments can be performed at
UF6 densities and temperatures that are
nearly the same as those for a full-scale
U F _ Dimer
plant. The only scaling required is increasing
the area of the gas flow and the
cross-sectional area of the irradiation zone.
SELECTIVE PHOTODISSOCIATION OF
UFt. After expansion through the nozzle, the
cooled gas is irradiated by a sequence of
infrared and ultraviolet laser pulses (Fig. 18).
Either one or two infrared lasers tuned in the
Fig. 18. The Los Alamos uranium enrichment scheme involves irradiating ex-
16-micrometer range provide selective vibra- pantion-cooled gas with infrared and ultraviolet lasers. The expansion super-
ti o n a 1 e x i a ion of 2 3 5 u F 6. ~h e cooling produces a substantial density of UF6 monomers at low temperature. Two
two-frequency infrared excitation described iirfrared lasers selectively excite the V3 vibrational mode of^m6molecules, and the
above provides higher selectivity than sin- excited molecules are dissociated by an ultraviolet laser. The UF5 product forms
g l e - f r e q u e n c y e x c i t a t i o n . T h e first particulatesthatareeasilyseparatedfromthegasflow.

Gas Flow
ûF6 and thereby increase the infrared

selectivity even further.
The infrared excitation produces a change
in the ultraviolet dissociation spectrum simi-
lar to that shown previously for CF31.Thus,
an ultraviolet laser tuned near the
low-frequency edge of the dissociation spec-
trum of unexcited molecules will provide
large dissociation yields for ûF6 and small
dissociation yields for ûF6. In addition,
ultraviolet dissociation of UF6 to UF5 is very
efficient, occurring with a near unity quan-
loact Plate tum yield in the 200- to 300-nanometer
wavelength region.
Although ultraviolet dissociation has been
chosen for the Los Alamos uranium enrich-
ment process, the intensity of the second
infrared laser can be increased to provide
dissociation without an ultraviolet laser. At
present both methods are being considered.
POSTPHOTOLYSIS CHEMISTRY AND

COLLECTION OF ENRICHED PRODUCT.
A primary concern regarding this stage of
the process was whether the UF5 and UF6
molecules might exchange fluorine atoms
Fig. 19. Cross-sectional view of sonic impactorfor collection of emkhedproduct. The before being separated. But the UF5
molecules rapidly form dimers in the super-
moleculesformed by dissociation of UFr aggregate to more massive particulates
sonic flow; these dimers are relatively im-
that are separated porn the gas /low in the sonic impactor. The gas reaches sonic
mune to exchange of fluorine with UF6.
velocities as it passes through small holes in the orificeplate and then bends around to
After being irradiated, the process gas
the exit port. The massive UF5 particulates cannot negotiate the bend and instead
containing the enriched UFi first passes
collect on the impact plate.
through a supersonic diffuser, which returns
the gas to higher pressure and room tem-
low-intensity laser is tuned near the resonant some ûF6 molecules. But the probability perature. The enriched material in the form
frequency of the ûF6 Q branch, and the for ultraviolet dissociation is substantially of particulates is then separated from the gas
second high-intensity laser is tuned far to the higher for the highly infrared-excited ûF6 stream and collected on a simple sonic
red of this peak to achieve maximum excita- molecules than for the ^ U F ~ molecules. The impactor (Fig. 19). The gas reaches sonic
tion of the "'uF6 molecules. Since multi- physics of the infrared excitation is complex velocities as it passes through a series of
ple-photon excitation can occur over a fairly and depends on a number of parameters. small orifices in a flat plate. At the exit of the
wide range of frequencies, especially at high These parameters are now being system- orifice plate the gas flow bends around to an
intensity, the second laser will also excite atically varied to minimize excitation of exit port. The massive particulates traveling
LOS ALAMOS SCIENCE

at sonic velocities cannot negotiate the turn
and impact on a backing plate. A typical run
time for a collection experiment is 1 to 2
hours. Figure 20 shows a sample of enriched
material collected on the impact plate.
DIAGNOSTICS. The samples collected from

this system constitute the major source of
d a t a a n d confidence for projected
performance of a full-scale plant. Each col-
lection experiment yields an enrichment pa-
rameter for one set of operating conditions,
but such experiments give little information
about the intermediate steps of infrared ex-
citation, ultraviolet dissociation, and post-
photolysis chemistry. Morever, collection ex-
periments are time-consuming and ex-
pensive. We have therefore developed a Fig. 20. Sample of enriched material produced by laser irradiation of UF6 gas and
real-time diagnostic technique that does not collected in a sonic impactor.
involve an assay of the solid material.
Based on detection of the fluorescence
induced in UF6 by a low-intensity ultraviolet enriched with this technique, that high values In 1976 milligram amounts of slightly
laser, the technique (Fig. 21) directly meas- of 6 can be achieved, and that the enriched enriched uranium were produced at Los
ures the number density of UF6 before and materical can be collected with little or no Alamos by the molecular laser isotope sepa-
after photolysis and thus the number density degradation by postphotolysis processes. ration process. Since then the major ex-
of UF, produced during photolysis. Experi- But the process must not only work-it perimental efforts have focused on increasing
ments are performed separately on each must work efficiently and economically. The a and 0 for this process. But these two
isotopic species as a function of the in- two parameters used most often to charac- parameters are not independent. For exam-
tensities and frequencies of the infrared and terize the figure of merit for an isotope ple one can increase 6 by increasing the
ultraviolet lasers and other important param- separation process are 6, the cut, and a, intensity of either the infrared or the ul-
eters. With this technique we have obtained another measure of enrichment. The cut is traviolet laser, but this increased intensity
many of the fundamental data about vibra- the fraction of UFi dissociated at each stage will saturate and broaden the absorption
tionally enhanced photodissociation of UF6. of enrichment. Obviously the larger the cut features and thereby reduce the selectivity
From the ratio of the enhanced dissociation and enrichment, the fewer the number of and decrease a.
for the two isotopes we can also project the stages needed in a full-scale plant. The The process parameters that determine a
intrinsic enrichment attainable for uranium enrichment parameter a, unlike 3, depends and 0 include the frequencies and intensities
with the molecular laser isotope separation on the cut. For enrichment in uranium-235 it of the lasers and the temperature of the UFo
process. is defined by gas. Currently, enrichment experiments are
aimed at determining a set of parameters
RESULTS OF THE URANIUM ENRICH- that optimize a and 0. Values for a and 6
MENT EXPERIMENTS. The collection and achieved in the experiments to date show
laser-induced fluorescence experiments clear- that the molecular laser isotope separation
ly show that vibrational excitation of UF6 process is economically competitive with
produces enhanced ultraviolet photodissocia- The economics of the process improves as a other separation methods. But since the
tion of the molecule, that uranium can be and 9 increase. entire parameter space has not been studied
LOS ALAMOS SCIENCE

Fluorescence
Signal
UV Laser
-
Gas Flow
IR Laser
Fig. 21. Real-time diagnostic technique for determining the high-gainphotomultiplier before and after the volume has been
number density of produced during photolysis. A irradiated by the infrared and ultraviolet laser pukes. The
low-intensity dye laser induces fluorescence in the difference is a direct measure of the produced during
molecules within a small volume about I centimeter h w n - photolysis. In experiments using this diagnostic technique, the
stream of the photolysis zone. Thefluorescence is detected by a infrared laser beam can befocused to provide highfluences.
(in particular, the selectivity of the multi- undertaken the engineering design studies discuss some aspects of the scaling involved
ple-photon process as a function of laser needed to convert a small-scale laboratory in our concept of a production plant and
frequency and intensity and UFx tern- experiment into a full-scale production plant. then briefly describe the intermediate-scale
perature is uncertain), additional work will In these studies we have specified the pro- facilities.
be required before we know with certainty duction plant in as much detail as possible,
SCALING UP. The performance goals for a
that we have achieved the optimal set of identified the scaling required, and designed
two intermediate-scale facilities in which production plant include the following.
operating parameters.
plant equipment can be developed and the o Product assay: 2 3.2%
Engineering Considerations process can be evaluated. One of these 0 Tails assay: < 0.1%
facilities, the preprototype, is now as- o Capacity: 8.75 MSWUIyear
Concurrent with the experimental re- sembled; the other, the demonstration mod- 0 Availability: 2 90%
search efforts to optimize a and 0, we have ule, is still in the design stage. We will first 0 Product cost: 5 $40/SWU
LOS ALAMOS SCIENCE

Fig. 22. Four major systems compose a production plant for here schematically is the organization of the more important
uranium enrichment by laser irradiation of UF6 gas. Shown equipment items and subsystems.
In more concrete terms a plant must produce tro-optical system, which includes the lasers strongly influences the design of the
an annual throughput of 1,500,000 kilo- and the beam-transport optics; the data photolysis chamber, as does the need to
grams of reactor-grade uranium, with tails acquisition and control system; and the minimize diffraction and other optical losses.
depleted t o 0.1 per cent, at a cost of about process support system. Figure 22 shows Other parameters influencing its design are
$600 per kilogram. Obviously, developing these systems schematically. the UF6 number density and the temperature
reliable plant equipment to meet these goals The design of a production plant begins and pressure of the process gas.
is not a trivial task. with the choice, guided by the product cost For the values of a and 0 believed to be
The equipment for a production plant can goal, of a n a and 0 combination. T o arrive at attainable, a plant must have not one but
be grouped into four major systems: the a product cost less than $40/SWU, current several photolysis chambers t o achieve the
process gas system, which includes the calculations show that a must be greater desired product assay. The chambers are
photolysis chambers and the components than 3 and 9 must be between 0.05 and 0.30, arranged in what is commonly referred t o as
providing the flow of process gas; the elec- depending on a. The choice of a and 9 an enrichment cascade (Fig. 23); the term

Cascade
Feed
Cascade Tails G 0.1% 2 3 5 ~
Fig. 23. Schematic gas flow pattern in an 11-stage cascadefor exiting to the righ or l$t)jlows to another stage for further
uranium enrichment by h e r irradhtion of m6gas. Each enrkhment, and the incrementally depleted stream from each
stage consists of a photolysk chamber and associated equip- stage flows to anuther stage for further depletion. This
ment. The relative volumetricjlow through a stage is indicated recirculatingjlow pattern avoids losses of separative work that
by the area of the rectangle representing the stage. The w o u occur
~ gstreams of unlike assay were mixed.
incrementally enrkhed stream from each stage (shown here
LOS ALAMOS SCIENCE

Fig. 24. Possible arrangement for integrating the h e r systems i@rared and ultraviolet h e r s service the entire cascade.
and the cascade stages in a production plant for uranium Interstage optics &just thefluences of the b e a m at each stage
enrichment by laser irradiation of m6gas. Single banks of of the cascade.
stage refers to a single chamber and its disposal system service the entire cascade. to higher energies by gangjng several laser
associated equipment. The number of stages All of the equipment necessary for the heads together in what is termed a master
in an enrichment cascade depends directly process gas system is within the current state oscillator power amplifier chain. Several
on the a and 0 combination chosen. In of the art. In particular, the flow equipment chains are necessary for each laser type.
general, low a and 0 values lead to a large developed for gaseous diflusion plants can be Individual high-energy beams must then be
number of stages, which in turn leads to translated in a relatively straightforward combined spatially to achieve the required
increased complexity, large size, high energy manner to a molecular laser isotope separa- beam area. T o irradiate all of the gas flowing
consumption, and high capital costs for the tion plant. through a plant-scale nozzle, the repetition
plant. The electro-optical system for a pro- rate of the laser pulses must be about 10,000
Each photolysis chamber in the cascade duction plant must be capable of uniformly hertz. Direct extrapolation of current tech-
includes a nozzle that might be as much as 8 irradiating the gas flow through each nology to achieve such high rates from a
meters wide, in contrast to the single 20-cen- photolysis chamber with the required in- single laser is not likely. However, the re-
timeter nozzle used in the laboratory experi- frared and ultraviolet laser fluences. The quired rate can be achieved by temporally
ments. Further, the gas flow though the laboratory experiments were performed with combining reliable, long-lived lasers with
c h a m k r s must be continuous rather than a small beam size and a low repetition rate repetition rates of about 1250 hertz. A
pulsed. Each stage must include a com- (about 1 hertz). Both these parameters must system known as a multiplexer combines the
pressor system for moving the gas and be increased considerably in a production laser beams temporally and a reflective mir-
equipment for collecting the enriched UF5, plant. ror arrangement called a dihedral combiner
converting it back to UF6, and returning it The required increase in beam area implies performs the spatial combination.
either to the cascade or to the final product a similar increase in beam energy to main- The electro-optical system must also com-
stream. A feed system, a gas purification tain the same fluence. The C 0 2 and XeCl pensate for the reduction in beam fluence
system, a tails removal system, and a waste lasers used in the experiments can be scaled that occurs as the beam progresses through
LOS ALAMOS SCIENCE

Sepurating Isotopes With Lusers
Fig. 25, The Laboratory's preprototype for testing the molecu- between that of the laboratory experiments and a production
lar h e r isotope separation process at a scale intermediate plant.
each photolysis chamber. This fluence reduc- ment for the process support system, such as equipment and each system. This level of
tion, which is due to absorption, degrades the cooling towers, gas liquefaction plants, and detail is suficient for reasonable costing, for
enrichment. It is not large, however, and can electrical power system, is standard and can studying design tradeoffs, and for establish-
be limited by restricting the width of the be obtained in the sizes required. ing the goals that can be achieved by scaling
photolysis chambers, In addition, the beam Integration of the cascade stages with the the process and the equipment.
transport system includes interstage optics electro-optical system is a major design and
that adjust the beam area to the required engineering problem. Figure 24 shows THE PREPROTOTYPE. Our first step toward
fluence as it is transmitted from one chamber schematically how this might be ac- a production plant was design and assembly
to the next. With this approach the laser complished. A typical production plant of a preprototype by the Laboratory's Ap-
beams can be adjusted to provide optimum might consist of two integrated cascades that plied Photochemistry Division. This facility
fluence at each stage of the cascade. share common subsidiary systems. will test the process and equipment at a scale
Data acquisition and process control for a We have carried out an extensive prod- significantly larger than that of the
plant demand no new technology, Existing uction plant design at a conceptual level. pulsed-flow experiments. The preprototype
computers and instrumentation can meet all That is, detailed design of equipment is (Fig. 25) includes a gas flow system capable
of the requirements for continuously bypassed in favor of an approach that clear- of continuous operation, lasers designed to
monitoring and controlling the elec- ly identifies the function, size, and operate at 1000 hertz, and a subscale
tro-optical and process gas systems. Equip- performance requirements for each piece of plant-type collector. The short lifetimes of
LOS ALAMOS SCIENCE

the switching elements in the laser systems design flexibility to permit their optimization
will limit the tests primarily to short-duration and refinement. A fully integrated stage will
(10-minute) runs. The gas flow area in the incorporate full-scale or directly scalable
preprototype is approximately five times hardware. Data on the performance, re-
greater than that in the pulsed recirculating liability, maintenance, and lifetime of the
loop. The repetition rate of the lasers is lasers will establish production plant design
suficient to irradiate only about 1 per cent criteria and realistic economic parameters.
of the available uF6. The preprototype
demonstrates that scaling the process gas Conclusions
system is straightforward and relatively inex-
pensive, but scaling the photon supply is
We have concentrated in this article on the
expensive and will require further engineer-
use of lasers to separate uranium isotopes.
ing.
The primary reason for pursuing the devel-
The preprototype will not address the
opment of a laser process for separating
requirements for spatial and temporal multi-
isotopes of any element is an economic one.
plexing, process staging, or interstage optics.
In the case of uranium the cost of the
Other issues not readily addressed by the
product from more conventional methods is
preprototype are gas cleanup requirements
high enough to warrant introduction of the
for recycling and propagation of the laser
more selective and technology-intensive laser
beams on a plant scale.
methods. We believe the high cost of the
photons involved can be offset by the reduc-
THE DEMONSTRATION MODULE. The tion in capital and operating costs and
questions of scale not addressed by the electric power consumption relative to con-
preprototype can be answered with our next ventional processes.
step toward a production plant, the demon- The intense research effort in this area has
stration module, The present plan is to led to significant advances in our fundamen-
complete the module in the late 1980s. It will tal knowledge of photon-molecule interac-
be capable of demonstrating all critical tions and in the technology of lasers. The
aspects of a production plant. Most optical application of this new knowledge and tech-
equipment and a beam transport system will nology t o more general areas in chemical
be demonstrated at plant design conditions. processing-selective chemical synthesis,
These components will be incorporated into purification, reaction-rate control, and
a muitinozzle configuration with suficient catalysis-has only just begun.
Further Reading
V. S. Letokhov and C. B. Moore*"Laser Isotope Separation," Soviet Journal of Quantum Electronics 6 ,

129- 150 and 259-276 ( 1976).
C. D. Cantrell, S. M.Freund, and J. L,Lyman, 'bLaser-Induced Chemical Reactions and Isotope

Separation," in Laser Handbook, Yo/. 111, M. L. Stitch, Ed. (North Holland Publishing Co., Amsterdam,,
1979).
V. S. Letokhov, "Laser-Induced Chemical Processes," Physics Today 33,34-41 (November 1980).
LOS ALAMOS SCIENCE

3 eparanng fsocopes wzut Lasers
AUTHORS
Reed J. Jensen received his Ph.D. in physical chemistry from Brigham

Young University in 1965. After a postdoctoral appointment at the
University of California, Berkeley, he joined the Laboratory's G M X
Division. Following a two-year teaching experience with Brigham Young
University, he returned to h s Alamos to initiate a program in chemical laser
research. He played a key role in advancing the technology of high-energy
pulsed chemical lasers. His experience with the interaction of laser radiation
and chemical kinetics led him duectly into the field of laser isotope
separation. During this period he, along with several coworkers, advanced
the concept for the molecular laser isotope separation process described in
this article. His promotion to the post of Assistant Division Leader of the
Laser Division was followed in 1976 by an appointment as Alternate
Division Leader of the newly formed Applied Photochemistry Division. In
1980 he was named Division Leader of the Applied Photochemistry Division
and Program Manager for molecular laser isotope separation. Under his
direction approximately 225 scientists and technicians pursued research and
development in laser isotope separation, laser-induced chemistry, applied
photochemistry, spectroscopy, and related fields. In I98 1 he was named
Deputy Associate Director for molecular laser isotope separation. (Photo by
LeRoy N. Sanchez)
O'Dean P. Judd received his Ph.D. in physics with a specialty in plasma
physics from the University of California at b s Angeles in 1968, For
several years he worked at the Hughes Research Laboratory on microwave
electronics, plasma physics, and high-energy lasers. He joined the Labora-
tory's Theoretical Division in 1972 as an Associate Group Leader of its
Laser Theory Group. There he did theoretical work on atomic and molecular
physics, lasers, and nonlinear optical interactions for the laser fusion and
laser isotope separation programs. In 1974 he became Group Leader of the
Laser Division's Advanced Laser Group, whose task was the development of
high-energy visible and ultraviolet lasers. In 1977 he joined the Applied
Photochemistry Division Office and worked on problems related to uranium
isotope separation and multiple-photon excitation processes in polyatomic
molecules. Currently he is a Project Manager for high-energy laser concepts
in the Defense Science and Technology Ofice. He is a consultant on lasers to
the National Oceanic and Atmospheric Administration and is an Adjunct
Professor of Physics in the Institute of Modern Optics and the Department
of Physics and Astronomy at the University of New Mexico. His theoretical
and experimental interests include lasers and quantum electronics, nonlinear
optics, atomic and molecular physics, plasma physics, and laser chemistry.
(Photo by LeRoy N. Sanchez)
J, Allan Sullivan earned a Bachelor of Science and a Master of Science in

aeronautical engineering from the University of Colorado. After receiving a
Ph.D. in mechanical engineering from the University of Michigan, he served
for a short time as an Assistant Professor at Colorado State University and
then joined the Laboratory in 1966. In his first few years with the
Laboratory, he worked on advanced nuclear reactor concepts and computer
codes for transient reactor behavior. In association with C, P. Robinson, he
helped pioneer some of the early research in laser development and isotope
separation at the Laboratory. In 1974 he was appointed Group Leader of
what is now the LIS Engineering Group in the Applied Photochemistry
Division. This group worked on advanced engineering for the then fledgling
molecular laser isotope separation program. In I977 he served a short time
as the Alternate Director for the Reactor Behavior Division of EG&G,
Idaho Falls and then returned to the Laboratory's Applied Photochemistry
Division. There he served as a project leader for novel instrumentation
applications of lasers and as an industrial liaison oficer. In 1980 he was
assigned to the Department of Energy's Office of Advanced Isotope
Separation where he represented the L,aboratory9s interests in formulating
the criteria for deciding which advanced isotope separation technology will
be scaled to production facilities. At present he is the Program Manager for
engineering implementation of the molecular laser isotope separation pro-
gram. (Photo by LeRoy N. Sanchez)
LOS ALAMOS SCIENCE

Laser Uranium Separation

Uploaded by

Copyright:

Available Formats

Laser Uranium Separation

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Laser Uranium Separation

Uploaded by

Copyright:

Available Formats

Based on recent discoveries in science and advances

s ince the advent of lasers, these

LOS ALAMOS SCIENCE

LOS ALAMOS SCIENCE

light. (3) One of the vibrational transitions indicated in (a) is of ""UF~.

LOS ALAMOS SCIENCE

LOS ALAMOS SCIENCE 5

6 LOS ALAMOS SCIENCE

LOS ALAMOS SCIENCE 7

LOS ALAMOS SCIENCE

\ \ Excited-State Potential Curve

PREDISSOCIATION. The usual photo-

w Isotopically Distinct Vibrational Levels

LOS ALAMOS SCIENCE 9

tion of carbon- 13 greater by a factor of 3 or Selective Vibrational Excitation

LOS ALAMOS SCIENCE

quires an ultraviolet photon with an energy,

LOS ALAMOS SCIENCE

MULTIPLE-PHOTON DISSOCIATION. Fig-

LOS ALAMOS SCIENCE

LOS ALAMOS SCIENCE

LOS ALAMOS SCIENCE

Fig. 10. Comparison of the high-intensity multiple-photon dissociation probability

LOS ALAMOS SCIENCE

LOS ALAMOS SCIENCE

The first step in this process, selective

LOS ALAMOS SCIENCE 19

20 LOS ALAMOS SCIENCE

LOS ALAMOS SCIENCE 21

EXPANSION SUPERCOOLING OF UF6.

LOS ALAMOS SCIENCE

The major question concerning this cool-

LOS ALAMOS SCIENCE

2. Resonant Infrared Excitation of 2 3 5 ~ ~ 6

accomplished in a blowdown mode in which

Despite the slow turnaround time, this setup

24 LOS ALAMOS SCIENCE

^uF6 and thereby increase the infrared

POSTPHOTOLYSIS CHEMISTRY AND

LOS ALAMOS SCIENCE

DIAGNOSTICS. The samples collected from

LOS ALAMOS SCIENCE

LOS ALAMOS SCIENCE

28 LOS ALAMOS SCIENCE

Cascade Tails G 0.1% 2 3 5 ~

LOS ALAMOS SCIENCE

LOS ALAMOS SCIENCE

LOS ALAMOS SCIENCE

V. S. Letokhov and C. B. Moore*"Laser Isotope Separation," Soviet Journal of Quantum Electronics 6 ,

C. D. Cantrell, S. M.Freund, and J. L,Lyman, 'bLaser-Induced Chemical Reactions and Isotope

V. S. Letokhov, "Laser-Induced Chemical Processes," Physics Today 33,34-41 (November 1980).

LOS ALAMOS SCIENCE

Reed J. Jensen received his Ph.D. in physical chemistry from Brigham

J, Allan Sullivan earned a Bachelor of Science and a Master of Science in

LOS ALAMOS SCIENCE

You might also like