Atomic Energy, Vol. 104, No.

5, 2008

INVESTIGATION OF 235UF6 AND 238UF6 SPECTRA

IN THE MID-IR RANGE

G. Yu. Grigor’ev,1 A. S. Lebedeva,1 UDC 535.34:539.19

S. L. Malyugin,1 Sh. Sh. Nabiev,1
A. I. Nadezhdinskii,2 and Ya. Ya. Ponurovskii2

A diode laser is used to measure the absorption spectra of 238UF6 and 235UF6 molecules in the composite
vibrational band ν1 + ν3 at wavelength λ = 7.68 µm. To determine the possibility of measuring the isotopic
ratio 235UF6 / 238UF6 with the required accuracy, the absorption coefficients of isotopic samples of 235UF6
and 238UF6 are measured, and the sources of errors and ways to minimize them are determined.

The isotopic composition of uranium hexafluoride, found in the chemical form UF6, is measured in separation plants
to a high degree of accuracy using gamma spectrometers and specialized mass spectrometers [1]. But at the same time a suf-
ficiently reliable, accurate, and rapid method for evaluating the degree of enrichment of UF6 when checking research labo-
ratories and facilities which are under IAEA control is not available.
At the present time, diode laser spectroscopy is one of the most promising rapid methods of isotopic analysis for
obtaining reliable information about the degree of enrichment of UF6 [2]. An important feature is its high sensitivity and
resolving power, and the possibility of tuning the wavelength of the laser radiation smoothly makes it possible to measure the
isotopic composition of atoms and molecules containing stable and radioactive nuclei [3, 4].
The fundamental possibility of using laser spectroscopy for fast analysis of the degree of enrichment of UF6 was
shown in [5, 6], where the IR spectra obtained for uranium hexafluoride by Fourier transformation were analyzed and the
choice of the lasing frequency in the mid-IR range at the wavelength λ = 7.68 µm was substantiated. The IR absorption spec-
tra of UF6 with the natural isotopic composition were studied using such a laser in the range of the composite vibrational
band ν1 + ν3. The absorption coefficient in this band is 500 times lower than the absorption coefficient in the ground vibra-
tional band ν3 but it is sufficient for measuring the IR absorption spectra in 10–20 cm long cells. On the basis of these spec-
tra and the known isotopic shaft of the ν3 vibration of UF6 molecules, model spectra were calculated for the two isotopic
modifications 238UF6 and 235UF6. However, the accuracy with which the degree of enrichment of UF6 is determined on the
basis of the model spectra was found to be too low for measuring the isotopic composition of uranium under real conditions
[6]. To increase the accuracy with which the isotopic ratio 235UF6/238UF6, it is necessary to know the real spectroscopic char-
acteristics of UF6 molecules with different isotopic composition.
In the present work, the IR absorption spectra of 235UF6, 238UF6, and mixtures of these compounds are studied
experimentally in the region of the composite vibration ν1 + ν3 using a λ = 7.68 µm diode laser. Special attention is focused
on the measurement of the absorption cross sections of the two isotopic modifications of uranium hexafluoride 238UF6 and

1
Russian Science Center Kurchatov Institute.
2
A. M. Prokhorov Institute of General Physics, Russian Academy of Sciences.

Translated from Atomnaya Énergiya, Vol. 104, No. 5, pp. 302–306, May, 2008. Original article submitted February
27, 2008.

398 1063-4258/08/10405-0398 ©2008 Springer Science+Business Media, Inc.

 Fig. 1. A block diagram of the experimental setup: 1) diode laser in a cryostat; 2, 8) photodi-
odes in reference channels; 3) reference gas cell; 4) Fabry–Perot etalon; 5) analytical gas cell;
6, 11) photodiodes in the analytical channels; 7) laser diode module for HF; 9) fiber-optic
divider; 10) reference laser cell for HF; DL1, DL2 – 7.68 and 1.283 µm wavelength diode
lasers, respectively; PD – photodiode; PA – pre-amplifier; DTB – data-transfer busses; PC –
personal computers.

235
UF6. This will make it possible in the future to determine the degree of enrichment of unknown samples with adequate
accuracy.
Experimental Procedure. An experimental setup consisting of a diode laser spectrometer and a vacuum-gas bench
for sample preparation was developed to study the absorption spectra of 238UF6 and 235UF6. The corrosion-resistant steel
bench included vessels for storing 235UF6, 238UF6, F2, and inert gases and sensors for measuring pressure and temperature.
The valve seals and other components of the bench were made of teflon. Since UF6 is highly active chemically and interacts
actively with the inner surface, the bench, the connecting pipeline, and the optical cells were carefully passivated with molec-
ular fluorine and 238UF6 at pressures 6.7–9.3 and 2–2.7 kPa, respectively, over a period of 6–10 days. The 238UF6 pressure
in the bench and the cells was maintained at 1.3 kPa in the intervals between measurements. Before each experiment was
started, the UF6 sample was additionally purified by a cryogenic method (successive freezing at −55°C, evacuation, and thaw-
ing at 20–25°C).
It is known that HF always forms in volumes where uranium hexafluoride is present or has been present, because of
its interaction with condensate water on the inner surfaces of the bench and analytical cells and with the water vapor in atmo-
spheric air, which with time flows into the volume of even well-evacuated vessels. The presence of HF in a sample gives rise
to an error when measuring the isotopic composition, i.e., the ratio 235UF6/238UF6. For this reason, the HF concentration was
measured during cleaning immediately before each experiment. The experiments showed that at least 0.1–0.2 vol.% HF
was present in the UF6 sample even after cryogenic cleaning. Thus, the uranium hexafluoride partial pressure is measured
with an error, which can result in an error in determining the isotopic ratio 235UF6/238UF6.
The 200 mm long and 25 mm in diameter optical cells were made of corrosion-resistant steel. BaF2 plates with 40 mm
diameter and a 3–5 sec tapering were used for the windows of the cell in order to eliminate interference of the laser radia-
tion. The windows were sealed with gaskets made of viton or fluoridated resin placed in special teflon pockets to minimize

399
 Fig. 2. Radiation frequency versus time when the laser is excited by the pump current pulse (a) and calibration of the
lasing frequency according to the reference channel (b).

the interaction of the windows with UF6. The cells were equipped with a cooled “finger” for condensation of samples of
235
UF6 and 238UF6 and their mixtures.
Figure 1 displays a block diagram of the diode laser spectrometer. The analytical channel of the spectrometer con-
sisted of a diode laser manufactured by Laser Components (Germany), a cell holding the experimental gas, and a photode-
tector. The laser, placed in a cryostat, was cooled with liquid nitrogen and could be continuously tuned near the maximum of
the UF6 absorption band ν1 + ν3 (λ = 7.68 µm). The average power of the radiation was 300 µW, and the width of the lasing
line was 5·10−4 cm−1. The laser was pumped with 750 mA trapezoidal current pulses with duration 3–5 msec. The pulse rep-
etition frequency was 250 Hz.
A cell with C2H2, CH4, or their mixture was present in the reference channel. A germanium Fabry–Perot etalon with
a free dispersion range 0.125 cm−1 was used to calibrate the frequency scale of the laser. The tuning curve for the working
regime, used for detecting the 235UF6 and 238UF6 spectra, is presented in Fig. 2a. The HITRAN spectral database [7] was
used to determine the tuning range of the laser 1289.66–1292.36 cm−1 experimentally. Figure 2b shows the absorption spec-
trum of uranium hexafluoride and the absorption lines of acetyline and methane, which were used to stabilize the tempera-
ture of the diode laser and for absolute referencing of the frequency scale of the absorption spectra of UF6.
HgCdTe photodiodes, manufactured by Kolmar Technologies Inc. (USA), were used as photodetectors. They were
placed inside liquid nitrogen cooled cryostats. Testing a photodiode at the wavelength 7.68 µm showed its detection power to
be D* = 3·1010 cm·Hz1/2/W.
The degree to which HF was removed from UF6 in the analytical cell was monitored with a laser module which
included a tunable Fabry–Perot etalon and a diode laser with distributed feedback and fiber-optic radiation output, which
emitted near the wavelength 1.283 µm (2-0 R0 HF line). The diode laser operated in a periodic-pulse regime: pulse duration
1–3 msec and repetition frequency to 1 kHz. An additional reference channel was used to tune the laser. The measurable HF
concentration threshold in a 200 mm long cell was less than 1 ppb.
A16-bit multifunctional board DAC/ADC NI PCI-6052E, manufactured by National Instruments Co. (USA), was
used to control the laser pumping, the temperature stabilizing systems, and signal detection and subsequent signal process-
ing. The operation of the diode laser spectrometer was controlled with the graphical programming language LabView 8.2
using National Instruments drivers.

400
 Fig. 3. Absorption spectrum of UF6 sample with the natural isotopic composition (a) and an 235UF6
enriched (~90%) sample (b) at pressures 1.4 (1), 2.8 (2), 4 (3), 5.3 (4), 6.4 (5), 1.3 (6), 2.7 (7), 4.2 (8),
5.3 (9), 6.6 (10), and 8 kPa (11).

Experimental Results and Discussion. Each series of experiments consisted of cycles of measurements of absorp-
tion by UF6 at different pressures. A baseline (transmission spectrum of an empty cell) was recorded before each series was
started. Next, these spectra were recorded at a definite UF6 pressure and after evacuation the transmission spectrum of the
empty cell was rerecorded. The measurement time for one series at each value of the UF6 pressure was no longer than sev-
eral minutes, which is a necessary condition for reaching the required accuracy.
Figure 3 shows that for the operating regime chosen the spectral range near the maximum absorption by 238UF6 is cov-
ered, while in the 235UF6 case this spectrum range is suboptimal. The presence of fine structure in the spectra is also evident.
Investigations showed that the optical zero and baseline can strongly influence the accuracy with which the UF6
absorption spectra are recorded. Specifically, a measurement error appears in the absorption coefficient as a result of noise in
the photodiode, preamplifier, and ADC as well as the nonresonance absorption by uranium hexafluoride sorbed on the cell
windows. The data presented in Fig. 3 were used to determine the absorption cross section of uranium hexafluoride gas. After
it was subtracted from the experimental spectra, the nonresonance absorption due to sorption of UF6 on the cell windows was
obtained (Fig. 4). It is evident that this absorption can reach several percent even after UF6 is evacuated from the cell; this is
important for the required experimental accuracy.
It is known [8] that the structure of the vibrational-rotational spectrum of a molecule is determined by the structure
of the vibrational-rotational levels of the molecule, the distribution of molecules over these levels (Boltzmann distribution at
equilibrium), and the transition dipole moments. In molecular spectroscopy, it is proved that the vibrational and rotational
motions of the molecules can be separated. The vibrational energy of a molecule depends on the nuclear masses, so that the
vibrational frequency undergoes an isotopic shift, which is clearly seen in Fig. 3. The shape of the spectrum is associated with
the rotational structural spectrum [9]. In the case of uranium hexafluoride, the uranium atom lies at the center of symmetry
of the molecule. For this reason, the mass of the uranium isotope does not affect, to a first approximation, the rotational
motion of the molecule. Hence it can be concluded that the spectra of the isotopic modifications of uranium hexafluoride are
identical to within the isotopic shift. This fact is confirmed in Fig. 5a, which displays the absorption cross-sections obtained
for 238UF6 and 235UF6 on the basis of data on the absorption cross-sections of the samples investigated.

401
 Fig. 4. Nonresonance absorption by uranium hexafluoride sorbed on the cell windows
at pressures 1.4 (1), 2.8 (2), 4 (3), 5.3 (4), and 6.4 kPa (5).

Fig. 5. 238UF6 (1) 235UF6 (2) absorption coefficients (a) and their difference (3) (b), which were
measured with the aid of a diode laser.

Analysis of the spectra of the absorption cross-sections of 238UF6 and 235UF6 made it possible to measure the iso-
topic shift of the composite vibration ∆ν = [ν1 + ν3(238UF6)] – [ν1 + ν3(235UF6)], which, in contrast to the isotopic shift of
the ground state vibration ∆ν = [ν3(238UF6)] – [ν3(235UF6)] = 0.65 cm−1, was equal to 0.59 cm−1. The difference of the
absorption spectra of the natural and enriched uranium hexafluoride samples can be used to determine the degree of enrich-
ment of unknown samples (Fig. 5b):

σ(ν) = R[σ5(ν) – σ8(ν)] + σ8(ν) = R∆σ(ν) + σ8(ν), (1)

where σ(ν) is the measured cross-section, R is the degree of enrichment, σ8(ν) and σ5(ν) are the absorption cross-sections of
238
UF6 and 235UF6, respectively, and ∆σ(ν) is the experimentally obtained difference of the absorption coefficients.
Equation (1) presumes that the effect of the 234UF6 present in the enriched sample on the shape of the spectrum is
negligible. However, additional investigations are needed, since even a negligible (at the level 1–2%) content of this isotope
can distort the measurements of real samples with unknown enrichment. For the case where 234UF6 is present, which is of
practical interest, a term which takes account of the absorption cross-section of 234UF6 must be introduced into Eq. (1).

402
 The spectra of specially prepared samples of enriched uranium hexafluoride with 235UF6 concentration ranging from
3.5 to 12%, which were measured with the diode laser spectrometer, were compared with the spectra obtained by the
mass-spectrometric method. It was found that when measuring enrichment the deviation from the mass-spectrometric data is
3–5% depending on the enrichment. Thus, this method is not as accurate as the mass-spectrometric method but it is more
accurate than the gamma-spectrometric method. Diode-laser spectroscopy has no competitors with respect to size and mea-
surement speed. It should be noted that new-generation of diode lasers with a wider tuning range (4–5 cm−1) will make it
possible to increase the measurement accuracy substantially.
In conclusion, it should be noted that IAEA inspectors can use the method based on diode laser spectroscopy for fast
evaluation of the degree of enrichment of UF6 but sorption of UF6 and its products of decomposition on the cell windows and
the presence of HF, which decreases the accuracy of measurements of the sample pressure, and inaccurate information about
the 234UF6 content in the sample must be taken into account in the course of the measurements and analysis of the results.
This work was supported in part by SCOPES 2005–2008 Grant JRP IB7320-110987.

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