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Line-mixing effect on NH3 line intensities

Article in Journal of Quantitative Spectroscopy and Radiative Transfer · November 2013

DOI: 10.1016/j.jqsrt.2013.04.021

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 Journal of Quantitative Spectroscopy & Radiative Transfer 130 (2013) 273–283

Contents lists available at ScienceDirect

Journal of Quantitative Spectroscopy &

Radiative Transfer
journal homepage: www.elsevier.com/locate/jqsrt

Line-mixing effect on NH3 line intensities

H. Aroui n, K. Ben Mabrouk, R. Boussassi
Laboratoire de Dynamique Moléculaire et Matériaux Photoniques, UR11ES03, Université de Tunis,
Ecole Supérieure des Sciences et Techniques de Tunis, 5 Av Taha Hussein, 1008 Tunis, Tunisia

a r t i c l e i n f o abstract

Article history: Line intensities belonging to nine branches of the ν2, 2ν2 and ν4 vibrational bands of
Received 5 December 2012 ammonia have been measured between 1000 and 2000 cm−1. The laboratory spectra at
Received in revised form room temperature (T ¼ 295 K) were recorded using a high-resolution Fourier transform
16 April 2013
spectrometer Bruker IFS 120 HR.
Accepted 18 April 2013
More than 460 lines with J≤12 were analyzed using a non-linear least-squares multi-
Available online 24 April 2013
pressure fitting procedure. The fits were performed with and without including the line
Keywords: mixing effects using 11 experimental spectra recorded at different pressures of pure NH3.
Line intensity On average the line intensities uncertainty is estimated to be 2%. The dependence of the
Ammonia
line intensities on the J and K quantum numbers is discussed. The effect of line mixing on
Line mixing
the line intensities is analyzed as a function of the rotational quantum numbers, of the
Transition moment
Coriolis interactions branches, and of the bands.
On average the values of line intensities obtained in the ν4 band when taking into
account line mixing have been found to be 6% smaller than those obtained using the Voigt
profile.
The transition dipole moments squared, determined for each line from the measured
intensities, exhibit significant rotational dependencies which are mainly caused by
vibration–rotation interactions. These moments are discussed as a function of vibrational
and rotational states. Finally the measurements are compared with previous measure-
ments and with values from spectroscopic databases.
The whole set of line intensities and transition dipole moments are given as supplementary
data for use in spectroscopic databases.
& 2013 Elsevier Ltd. All rights reserved.

1. Introduction atmospheric concentrations, high resolution molecular spec-

Infrared spectra of ammonia have been extensively
studied in the past in order to measure line positions,
line intensities, and pressure broadening coefficients [1–4].
Precise knowledge of these parameters is useful for the
interpretation of high resolution infrared spectra of terrestrial,
planetary, and stellar atmospheres. Ammonia has been
detected in the atmospheres of Jupiter [5] and Saturn [6],
and in the Earth's atmosphere [7]. In order to retrieve accurate
n
Corresponding author. Tel.: +216 71496066; fax: +216 71391166.
E-mail address: haroui@yahoo.fr (H. Aroui).
troscopy studies in laboratories are necessary for the improve-
ment of atmospheric databases [8–10].
An important number of studies at high resolution have
been published concerning the line intensities in several
bands of NH3. Markov et al. [11] have measured line
intensities in the ν1 and the ν3 bands using a difference
frequency laser. In Ref. [12] Pine and Dang-Nhu analyzed
the line intensities obtained in the Ref. [11] to derive band
strengths, transition moments and Herman–Wallis correc-
tion factors responsible of Coriolis interactions between
the ν1 and ν3 bands.
Nakanaga et al. [13] have obtained line strengths in the
P and R branches of the ν2 band using a Fourier Transform
(FT) spectrometer. The same experimental method has

0022-4073/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jqsrt.2013.04.021
274 H. Aroui et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 130 (2013) 273–283
been used by Fabian and Yamada [14] which have mea-
sured line intensities for a great number of transitions in
the ν2 band. They have deduced the transition dipole
moments and the Herman–Wallis parameters responsible
on the vibration–rotation interactions in this band. A
microwave sideband CO2 laser spectrometer was used by
Chu et al. [15] to measure the strengths of a series of lines
in the ν2 band. Hadded et al. [16] have measured line
intensities for some inversion doublets in the PP branch of
the ν4 band: in their work, the need to take into account
the line mixing effects in the determination of the line
parameters has been clearly demonstrated. Using a Voigt
profile and simple theoretical formulas derived by the
contact transformation method applied to the dipole
moment operator, Aroui et al. have measured line inten-
sities in the ν2 [17] and ν4 [18] bands of NH3 using an FT
spectrometer. From their intensity measurements, they
were able to determine transition dipole moments, band
strengths, and Herman–Wallis parameters for the ν2 and
ν4 bands.
Line intensities and self-broadening coefficients have
been determined for 20 transitions in the 2ν2 and ν4 bands
of NH3 using a diode laser spectrometer [19]. The forbid-
den Δk¼ 72 transition intensities in the v4 vibrational
state of NH3 have been measured from the FT spectra using
a multipass White-type cell [20]. These intensity data have
been analyzed using the contact transformation method.
Line intensities of 33 transitions in the ν4 band of 15NH3
have been measured using a diode laser spectrometer [21].
The interpretation, based on the third-order theory of line
strengths [22], yields transition moments and the band
intensity of the ν4 band. About 1000 line intensities of the
ν1, ν3, and 2ν4 bands of NH3 were measured and modeled
to 11 terms of the transition dipole moment expansion by
Kleiner et al. [23]. Their model allowed them to predict
about 2700 line intensities in these bands.
CO2 laser-microwave double resonance spectroscopy
was applied to determine the precise dipole moment in
the ground state of NH3 [24]. Line intensity calculations
were performed by Yurchenko et al. [25] for ammonia
spectra covering a large infrared region. Recently line
intensities of 22 ammonia transitions belonging to the ν2
fundamental band have been undertaken at different
temperatures using FT spectra [26]. From this non-
exhaustive list of previous studies, some of them will be
used in the present work to be compared with our new
measurements.
The goal of the present paper is to provide line
intensities for the ν2, 2ν2 and ν4 bands of 14NH3 at room
temperature, with particular focus on the effect of line
mixing on line intensities. More than 460 line intensities
have been measured in these bands using a high resolu-
tion FT spectrometer of the “Laboratoire de Photophysique
Moléculaire (LPPM)” in Orsay, France. A multi-pressure
fitting procedure [16] has been used to adjust a set of
spectroscopic line parameters until reproducing experi-
mental spectra. The transition dipole moments squared
were determined from the measured line intensities.
The absorption of ammonia in the studied spectral region
is mainly due to the ν2, ν4 and 2ν2 bands. Energy levels of the
v4 ¼ 1a state (antisymmetric levels) are pushed away from
the v4 ¼1s state (symmetric level) through Coriolis interac-
tions between the v4 ¼1a state and close-lying v2 ¼2s state.
Theses interactions cause drastic changes in line intensities
due to the presence of cross-terms in the transition dipole
moment operator [19].
The experimental and fitting procedures are described
in Sections 2 and 3, respectively. The line intensities and
the transition dipole moments squared are determined
as a function of J and K quantum numbers in Section 4.
Section 5 is devoted to the discussion and analysis of
the data.
2. Experimental details
The high-resolution Fourier transform spectrometer Bru-
ker IFS 120 HR was used to record self-perturbed spectra of
NH3 at room temperature (T¼29571 K) in the ν2, 2ν2 and ν4
bands covering the spectral range 1000–2000 cm−1. This
interferometer has a maximum optical path difference
(MOPD) of up to 473.68 cm (maximum resolution¼
0.0019 cm−1). This instrument has all the equipments
required to operate from the far infrared to the ultraviolet.
Here, it was equipped with a globar source, an MCT photo-
voltaic detector cooled with liquid nitrogen down to 77 K, a
KBr beamsplitter and an optical filter limiting the light to the
spectral region of 1000–2250 cm−1. The spectra were
recorded with an entrance aperture diameter of 1.15 mm, a
40 kHz scanner frequency, and an MOPD of 225 cm. Accord-
ing to the Bruker definition of spectral resolution, this MOPD
corresponds to a resolution of 0.004 cm−1 with a Gaussian
shape for the apparatus function.
The gas was contained in a stainless steel gas cell
equipped with CaF2 windows with a path-length of
ℓ ¼ 25 7 0:1 mm. Samples of ammonia in natural abun-
dances were provided by “Air Liquide France” with stated
purities of 98.5% and without further purification. Spectra
were recorded at a series of 11 pressures ranging from 6 to
142 mbar (6.0, 10.0, 15.0, 18.6, 31.0, 43.0, 61.0, 81.0, 98.0,
120.0, 142.0 mbar). The pressures of the gas were measured
accurately by employing three capacitance MKS Baratron
manometers. The accuracy of these calibrated manometers,
as stated by the manufacturer, is 0.5% of the readout.
With respect to the adsorption on the cell walls,
ammonia sample pressures were allowed to thermalize
and stabilize for sufficient time (while monitoring the
pressure in the cell) before the spectrum of the sample
was recorded, typically between a few minutes for high
pressures, and up to about several hours for low pressures.
All spectra were obtained by averaging 100 interferometer
scans with a signal-to-noise ratio of about 200. Every
interferogram was transformed into a spectrum using the
procedure included in the Bruker software OPUS package
[27] with the Mertz phase error correction method [28].
The number of spectra was chosen in order to have a
sufficient information on all line parameters when analyz-
ing a transition using the multi-pressure fitting procedure.
An overview of the detailed experimental conditions is
given in Table 1. Note that almost the spectra have
previously been used in Refs. [17,18,29] but without
including line mixing effect.
 H. Aroui et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 130 (2013) 273–283 275

Table 1
1.2
Listing of experimental conditions used in recording spectra of NH3 at a
temperature at T ¼ 295 K.
1.0
Experimental parameters Value
0.8

Transmittance
Resolution (cm−1) 0.004
Maximum optical path difference (cm) 225 0.6
Collimator focal length (mm) 418
Scanner frequency 40 kHz 0.4
Scan number 100
Aperture diameter (mm) 1.15 0.2
Useful spectra domain (cm−1) 1000–2000
NH3 pressure From 6 to 142 mbar
0.0
1600 1610 1620 1630 1640 1650 1660
Wavenumber (cm-1)
For all recorded spectra the entire optical path of the Fig. 1. Transmittance spectrum of NH3 in the region between 1593 and
spectrometer was continuously evacuated with a cryogenic 1665 cm−1 of the 2ν2 and ν4 bands at the pressure of 18.6 mbar.
pump to remove residual CO2 and H2O in the interferometer.
The transmittance at wavenumber s was calculated from the
measured intensities by the usual ratio of recordings with
and without the gas sample.
The observed data contain transitions of the ν2 parallel
and ν4 perpendicular fundamental bands centered at 950
and 1626 cm−1 respectively, and transitions of the 2ν2
parallel overtone near 1597.470 and 1882.179 cm−1 (for s
and a inversion states, respectively).
An entire transmittance spectrum of NH3 in the region
between 1000 and 2000 cm−1 is shown in Fig. 1 which
shows the ν2, 2ν2 and ν4 bands at the pressure of 18.6 mbar.
Fig. 2 represents a zoom of Fig. 1. It shows an overview of
transmittance spectrum in the ν4 band in the region between
1593 and 1665 cm−1.

Fig. 2. Whole transmittance spectrum of NH3 in the region between

3. Fitting procedure
A multi-pressure fitting procedure has been used to
retrieve line strengths by fitting 11 spectra recorded at
different pressures. This procedure consists of a nonlinear
least-squares method in which line parameters (position,
intensity, broadening, line mixing parameter and baseline)
were determined by fitting small interval frequency with
widths depending upon the complexity of the considered
region. A single run of a FORTRAN code is enough to fit
successively all sample pressures and to obtain these
parameters for each of the 11 spectra.
These spectra recorded at moderately low pressures
were analyzed by taking into account line mixing effects.
Within the impact theory of the spectral shape, the
collisional absorption coefficient α(s) is assumed to be
described by a Rosenkranz profile [30–34]:
P PY k ðs−sk Þ þ Pγ k
αðsÞ ¼ ∑ S ; ð1Þ
π lines k k ðs−sk Þ2 þ ðPγ k Þ2
where k represents the line viJiKi- vfJfKf, Sk its intensity in
cm−2 atm−1, sk its wavenumber in cm−1 including the
collisional shift, γk its broadening coefficient in cm−1 atm−1,
and Yk, in atm−1 is its line-mixing parameter. The fits of the
recorded spectra have been performed with (Yk≠0) and
without (Yk ¼0) taking into account line mixing effects.
Experimental transmittance spectra were analyzed
using the following expression which is a convolution of
1000 and 2200 cm−1 illustrating the three bands ν2, 2ν2 and ν4 bands
under pressure of 15 mbar. Wavenumbers around 1050 cm−1, 1550 cm−1
and 1750 cm−1 are assigned to the ν2, ν4 and 2ν2 bands.
the collisional absorption coefficient α(s) given by Eq. (1)
with the FT spectrometer apparatus function FApp and the
Doppler profile αDop.
Z þ∞
τC ðsÞ ¼ F App ðs−s′Þ
−∞
 Z þ∞ 
exp −ℓ αDop ðs′−s″Þαðs″Þds″ ds′ ð2Þ
−∞
The parameter deduced from the fits for a line k are γ k ,
sk , Sk , and Y k . These parameters have been iteratively
adjusted by the multi-pressure fitting procedure to obtain
the best agreement between the experimental and calcu-
lated absorption profile. This procedure can fit several
lines simultaneously. This was the case of several sets of
overlapped lines of the studied bands. Results concerning
self-broadening, line shifts and line mixing parameters
have been published in previous publications [29] for
about 330 lines of the ν2, 2ν2 and ν4 bands.
An example of multi-pressure fitting procedure with
and without including line mixing for four pressures in
the case of the aR(3,3) line of the 2ν2 band, and the two
R
components of the asR(4,4) inversion doublet of the
ν4 band at various pressures is shown in Fig. 3a and b.
276 H. Aroui et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 130 (2013) 273–283

R
Fig. 3. (a) Multis-pressure fits of pure NH3 spectra for the aR(3,3) line of the 2ν2 band, and the components of the asR(4,4) inversion doublet of the ν4 band
at various pressures. (—) and () are the measured and calculated spectra with the inclusion of line mixing effect. Residual (measured minus calculated)
R
spectra are shown in the lower part of graphs. The line center of the aR(3,3) line shifts toward higher frequencies, whereas the components of the asR(4,4)
are shifting toward each other. (b) The same as (a) but without the inclusion of line mixing effect showing large discrepancies between measured and
calculated spectra.

Measured minus calculated deviations are given in the
lower part of the plots. On the other hand these figures
illustrate the strong shifting of the line centers: the aR(3,3)
line center shifts toward higher frequencies, whereas the
R
two inversion components of the asR(4,4) are shifting
toward each other; they have opposite sign of shift. As
explained in Ref. [29], this mutual interaction is a char-
acteristic of line-mixing.
 H. Aroui et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 130 (2013) 273–283
In Fig. 3a, one can observe that at P¼ 10 mbar, for
example, taking into account line-mixing effects do not
improve significantly the fitted spectra since the pressure
is not high enough to allow the overlap of lines. However,
at higher pressures P ¼61, 98 and 142 mbar, we can see
obviously at Fig. 3b that fitting spectra without line-mixing
leads to an important residuals which are reduced sig-
nificantly when line-mixing effects are taken into account.
From these figures the need to take into account the line
mixing effects is clearly highlighted.
One can attempt to improve the precision of the dataset
and to reduce the fit residuals by taking Dicke narrowing
and speed-dependent broadening into account. These two
effects are neglected in this work because; as mentioned
by Pine and Markov [35], they are greatly masked by the
large self-broadenings of NH3 with a large dipole moment.
4. Line intensities and transition dipole moments
4.1. Line intensities
Plots of integrated intensities Sk (cm−2), derived from
the fit using the Rosenkranz profile given by Eq. (1) by
taking into account line mixing effects (Yk≠0), as a function
of the NH3 pressure P are shown in Fig. 4 for the PsP(2,1),
P P P P
s P(3,1), s P(4,1), s P(6,1) and s P(7,1) lines in the ν4 band. One
can observe that the straight lines, obtained from linear
least-squares procedures, go well through the measured
points. The line intensities S0 (cm−2 atm−1) are derived
from the slopes of these lines. In this graph for PsP(J,1) lines,
the maximum intensity is obtained for PsP(4,1) line with
J ¼4.
The measured line intensities in cm−2 atm−1 for 462 lines
in the PP, PQ, PR, RP, RQ and RR branches of the ν4 band, in the
R and Q branches of 2ν2 band as well as in the R branch of
the ν2 band are listed in Table 2 and in supplementary data.
Samples of these data concerning the PP branch of the
ν4 band are presented in Table 2.
In this Table we have listed for each line the rotational
assignment, the position frequency, and the measured line
intensity along with the estimated errors given in
Fig. 4. Pressure dependence of the intensity parameter S for the PsP(2,1),
P P P P
s P(3,1), s P(4,1), s P(6,1) and s P(7,1) lines in the ν4 band of NH3. The slopes
of fit line represent the line intensity. The maximum intensity is obtained
for PsP(4,1) with J¼ 4. In these graphs the line mixing effect is taken into
account.
277
parentheses. The assignments of the lines considered in
Table 2 and supplementary data are taken from Ref. [3] for
the 2ν2 and ν4 bands and from Ref. [36] for the ν2 band.
The main sources of uncertainties in the determination of
line intensity parameters arise from the perturbation due to
the baseline location, the line shape model used, the gas
purity, and the approximations done by accounting for
instrumental distortions. The results for some transitions
are not given since their profiles are significantly overlapped
by neighboring lines (NH3 or residual H2O lines). The mean
values of the accuracies are estimated to be about 2%, 4% and
3% for the ν2, 2ν2 and ν4 bands respectively evaluated as one
time standard deviation for all measured transitions in this
work. These experimental uncertainties vary widely depend-
ing on the quality of spectral lines, and less blended lines are
better fitted. It should be noted that for very few lines, the
accuracies can attain more than 5%.
When considering all error sources, one can evaluate
the estimated uncertainties as follows. The sample pres-
sure was measured with an accuracy of 0.5%. Taking into
account the adsorption and desorption of NH3, the corre-
sponding contribution to the total uncertainty is estimated
to 0.8%. The temperature variation during the spectrum
recording contributes to an intensity error of about 0.2%.
The contribution from the cell length (ℓ ¼ 25 7 0:1 mm)
uncertainty can be estimated to 0.4%. The zero-level
(determined at high pressure using few saturated lines in
the ν2 band), contributes to an error of about 0.5%. The
total estimated uncertainties are calculated as the square
root of the quadratic sum of the different errors.
An overview of Table 2 and supplementary data show
that, as expected, the 2ν2 line intensities are significantly
smaller than those of the ν2 and ν4. Those of the ν2 band are
much greater than those of the ν4 band. As may be seen in
Table 2 and supplementary data the intensities of transitions
with a nuclear spin statistical weight of the lower level gi ¼ 2
(K¼3n, n¼1, 2…) are larger than those with gi ¼1 with K≠3n.
4.2. Transition dipole moments
The measured line intensities have been used to derive
the transition dipole moments squared of the line under
study using the following expression [22]:
T Z S0 ðJ; KÞ
R2 ¼ ;
3054:8ð1 þ δK;0 Þgi sif exp½−EðJ; KÞ=kT½1−expðhcsif =kTÞHJK
ð3Þ
where Z is the total partition function, sif is the wavenumber
of the line under study, Kroneckers symbol δK,0 is used to
take into account the degeneracy of ΔK¼ 71 transitions
from rotational levels with K¼0, h is Planck's constant equal
to 6.6260755  10−27 erg s (1 erg¼10−7 J), c is the speed of
light in vacuum equal to 2.99792458  1010 cm s−1, k is the
Boltzmann constant equal to 1.380658  10−16 erg K−1, and
T¼295 K. HJK is the Höln–London factor whose expressions
depend on the branch under study. These expressions are
given in Ref. [22]. E(J,K) (in cm−1) is the lower rotational
energy of transition. Distinct E(J,K) values, computed using
the rotational constants of Refs. [3,36], have been used for
symmetric and asymmetric states.
278 H. Aroui et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 130 (2013) 273–283

Table 2
Line intensities (in cm−2 atm−1) and transition dipole moments squared R2 (in Debye2) of NH3 at T ¼ 295 K in the PP branch of
the ν4 band as a function of J and K quantum numbers. The values given in parentheses correspond to the estimated
uncertainties expressed as one time standard deviation.

Transition r0 (cm−1) S0 (cm−2 atm−1) R2 (Debye2)

v4 band—PP(J, K) branch

P
s P(1,1) 1610.1016 0.1792 (0.0018) 0.001664
P
a P(1,1) 1610.4090 0.1763 (0.0033) 0.001637
P
s P(2,1) 1590.6916 0.2651 (0.0022) 0.002016
P
a P(2,1) 1591.1050 0.2510 (0.0028) 0.001908
P
s P(2,2) 1594.7907 0.4846 (0.0051) 0.001741
P
a P(2,2) 1595.0801 0.4611 (0.0036) 0.001656
P
s P(3,1) 1571.8315 0.3007 (0.0023) 0.002320
P
a P(3,1) 1572.4882 0.3440 (0.0041) 0.002653
P
s P(3,2) 1575.8518 0.4563 (0.0046) 0.001996
P
s P(3,3) 1579.3615 1.3502 (0.0181) 0.001795
P
a P(3,3) 1579.6363 1.3322 (0.0156) 0.001771
P
s P(4,1) 1553.6294 0.3290 (0.0037) 0.003024
P
a P(4,1) 1554.7340 0.3683 (0.0034) 0.003383
P
a P(4,2) 1558.2494 0.4827 (0.0019) 0.002794
P
s P(4,3) 1560.8895 1.0930 (0.0120) 0.002062
P
a P(4,3) 1561.3835 1.0869 (0.0135) 0.002050
P
s P(4,4) 1563.8239 0.7524 (0.0083) 0.001874
P
a P(4,4) 1564.0824 0.7285 (0.0098) 0.001814
P
s P(5,1) 1536.2088 0.3012 (0.0023) 0.003780
P
a P(5,1) 1538.0102 0.3547 (0.0047) 0.004446
P
s P(5,2) 1539.7596 0.3660 (0.0042) 0.003102
P
a P(5,2) 1541.0041 0.3654 (0.0043) 0.003095
P
s P(5,3) 1542.9798 0.8191 (0.0064) 0.002376
P
a P(5,3) 1543.8550 0.8629 (0.0064) 0.002501
P
s P(5,4) 1545.8043 0.5262 (0.0063) 0.002090
P
a P(5,4) 1546.3315 0.5159 (0.0059) 0.002049
P
s P(5,5) 1548.1839 0.6731 (0.0079) 0.001816
P
a P(5,5) 1548.4290 0.6697 (0.0091) 0.001807
P
s P(6,1) 1519.6627 0.1855 (0.0020) 0.003269
P
a P(6,1) 1522.3847 0.1866 (0.0020) 0.003490
P
s P(6,2) 1522.7763 0.2468 (0.0034) 0.003394
P
a P(6,2) 1524.7088 0.2571 (0.0024) 0.003531
P
s P(6,3) 1525.7625 0.5695 (0.0092) 0.002781
P
a P(6,3) 1527.0615 0.6026 (0.0085) 0.002940
P
s P(6,4) 1528.3774 0.3435 (0.0040) 0.002364
P
a P(6,4) 1529.2897 0.3545 (0.0032) 0.002439
P
s P(6,5) 1530.6141 0.4446 (0.0047) 0.002128
P
a P(6,5) 1531.1591 0.4484 (0.0049) 0.002145
P
s P(6,6) 1532.4503 1.1720 (0.0154) 0.001915
P
a P(6,6) 1532.6830 1.1845 (0.0135) 0.001936
P
s P(7,1) 1504.0218 0.1656 (0.0026) 0.005560
P
a P(7,2) 1509.4479 0.1716 (0.0018) 0.004235
P
s P(7,3) 1509.1379 0.3476 (0.0032) 0.003141
P
a P(7,3) 1511.3131 0.3757 (0.0033) 0.003390
P
s P(7,4) 1511.5985 0.1828 (0.0029) 0.002383
P
a P(7,4) 1513.0439 0.2619 (0.0018) 0.003412
P
s P(7,5) 1513.6480 0.2387 (0.0026) 0.002206
P
a P(7,5) 1514.6055 0.2384 (0.0038) 0.002202
P
s P(7,6) 1515.3243 0.6602 (0.0039) 0.002080
P
a P(7,6) 1515.8819 0.6535 (0.0115) 0.002100
P
s P(7,7) 1516.6309 0.4763 (0.0051) 0.002073
P
a P(7,7) 1516.8521 0.4203 (0.0045) 0.001829
P
a P(8,1) 1494.2421 0.0978 (0.0008) 0.006327
P
s P(8,3) 1493.5269 0.2073 (0.0011) 0.003815
P
a P(8,3) 1496.1740 0.2361 (0.0026) 0.004337
P
s P(8,4) 1495.5200 0.1087 (0.0034) 0.002943
P
a P(8,4) 1497.6750 0.1285 (0.0015) 0.003474
P
s P(8,5) 1497.3332 0.1475 (0.0009) 0.002878
P
a P(8,6) 1499.8082 0.3447 (0.0027) 0.002367
P
s P(8,7) 1499.9436 0.2202 (0.0017) 0.002078
P
a P(8,7) 1500.5103 0.2347 (0.0021) 0.002214
P
s P(8,8) 1500.7334 0.2879 (0.0026) 0.001815
P
a P(8,8) 1500.9439 0.2851 (0.0030) 0.001797
P
s P(9,1) 1475.3354 0.0495 (0.0005) 0.006900
P
a P(9,1) 1481.5769 0.0527 (0.0009) 0.007316
P
s P(9,2) 1476.8723 0.0506 (0.0004) 0.005472
 H. Aroui et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 130 (2013) 273–283 279

Table 2 (continued )

Transition r0 (cm−1) S0 (cm−2 atm−1) R2 (Debye2)

v4 band—PP(J, K) branch

P
a P(9,2) 1482.0589 0.0516 (0.0004) 0.005560
P
s P(9,3) 1478.1271 0.1020 (0.0015) 0.004208
P
a P(9,3) 1482.6879 0.1155 (0.0012) 0.004750
P
s P(9,4) 1480.1830 0.0524 (0.0016) 0.003232
P
a P(9,4) 1483.2433 0.0644 (0.0001) 0.003964
P
s P(9,5) 1481.7127 0.0749 (0.0008) 0.003377
P
a P(9,5) 1483.9454 0.0638 (0.0022) 0.002729
P
s P(9,6) 1482.9502 0.1697 (0.0014) 0.002729
P
a P(9,6) 1484.5122 0.2012 (0.0019) 0.003232
P
s P(9,7) 1483.8750 0.1157 (0.0024) 0.002464
P
a P(9,7) 1484.8947 0.1029 (0.0027) 0.002371
P
s P(9,8) 1484.4804 0.1529 (0.0085) 0.002306
P
a P(9,8) 1485.0539 0.1484 (0.0022) 0.002374
P
s P(9,9) 1484.7660 0.3733 (0.0090) 0.001833
P
a P(9,9) 1484.9662 0.3775 (0.0071) 0.001813
P
s P(10,1) 1462.1902 0.0222 (0.0004) 0.007362
P
s P(10,2) 1463.2914 0.0248 (0.0004) 0.006502
P
a P(10,3) 1471.6211 0.0394 (0.0003) 0.003985
P
s P(10,4) 1465.6044 0.0273 (0.0006) 0.004210
P
s P(10,5) 1466.8205 0.0404 (0.0016) 0.004612
P
s P(10,6) 1467.7783 0.0735 (0.0011) 0.003026
P
s P(10,7) 1468.4593 0.0458 (0.0007) 0.002647
P
a P(10,9) 1469.5219 0.1575 (0.0026) 0.002050
P
s P(11,2) 1450.5127 0.0098 (O.0002 0.006860
P
a P(11,3) 1458.1027 0.0209 (0.0006) 0.005725
P
a P(11,4) 1457.1906 0.0109 (0.0004) 0.004591
P
s P(11,6) 1453.3192 0.0356 (0.0030) 0.004107
P
s P(11,7) 1456.0695 0.0201 (0.0008) 0.003281
P
s P(11,10) 1453.3409 0.0425 (0.0013) 0.002058
P
s P(11,11) 1452.6522 0.0776 (0.0018) 0.002347
P
a P(11,11) 1452.8327 0.0757 (0.0010) 0.002289

Using this equation and the measured values of line 0.22

intensities in Table 2 and in supplementary data, we have 0.20
determined the transition dipole moments squared as a 0.18
function of rotational quantum numbers for the ν2, 2ν2 and 0.16
ν4 bands. The results are presented in Table 2 and supple-
0.14
mentary data for all branches considered in this work.
S0(cm-2 atm-1)

0.12

0.10 R(4,K)
5. Analysis and results 0.08

0.06 R(5,K)

5.1. Rotational dependencies of the line intensities 0.04 R(6,K)

0.02
We discuss in the following the J and K rotational quantum R(7,K)
0.00 R(8,K) R(9,K)
numbers dependencies of line intensities S0 and transition
dipole moments squared R2. As seen by Table 2 and supple- 0 2 4 6 8 10

mentary data the S0 of the PP, PQ and RR branches of the ν4 K

band, as well as those of Q and R branches of ν2 and 2ν2 bands
seem to increase with K for a given J when dividing by 2 the
line intensities for K¼3n. For example, in the ν4 band, the
S0 ¼1.172070.0154 cm−2 atm−1 of the PsP(6,6) transition is
greater than the value S0 ¼0.444670.0047 cm−2 atm−1
obtained for the PsP(6,5) line. This behavior can be seen clearly
in Fig. 5 where intensities of some manifolds of the R branch
in the 2ν2 band are displayed versus K at given J. However
when K is close or equal to J, line intensities of some manifolds
exhibit a slight decrease. For the other branches (PR, RP and RQ
of the ν4 band) S0 values appear to decrease with K.
Table 2 and supplementary data illustrate also that for all
branches of the three bands, the line intensities present a
Fig. 5. Intensities (in cm−2 atm−1) of R(4,K), R(5,K), R(6,K), R(7,K), R(8,K)
and R(9,K) manifolds of the 2ν2 band as a function of K quantum number.
Intensities of the lines with K¼ 3n, having a nuclear statistical weigh
gi ¼2, are divided by 2.
maximum around J¼4 for Ko4. Fig. 6 shows this trend for
the R branch of the ν2 band. This may be understood, since
line intensity is proportional to the factor HJK exp½−EðJ; KÞ=kT
which could present a maximum with J position depending
on K. For K≥4, the S0 values decrease monotonically with
increasing J. There are some exceptions for this behavior, the
S0 values appear to decrease monotonically with J for the RR
and Q branches of the ν4 and 2ν2 bands respectively.
280 H. Aroui et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 130 (2013) 273–283
R(J,1)
S0(cm-2 atm-1)
R(J,2)
2 R(J,3) R(J,4)
R(J,5)
1 R(J,6) R(J,9)
R(J,7)
R(J,8)
0
0 1 2 3 4 5 6 7 8 9
J folds of the 2ν2 band as a function of K quantum number for J¼ 4-9.
Fig. 6. Intensities (cm−2 atm−1) of the R(J,K) manifolds of the ν2 band as a
function of J quantum number for K¼ 1-9.
Fig. 7. Transition dipole moments squared R2(Debye2) for the RsR(J,K)
manifolds of the ν4 band as a function of J quantum number for K¼ 1, 2, 3,
5, 6 and 9.
Furthermore Table 2 and supplementary data show
that the line intensities of the symmetric lines are slightly
larger than those of the antisymmetric ones. The differ-
ence between these intensities increases with the splitting
between the doublets components. This is the case for
almost all lines of the ν4 band. Note that for the ν2 and 2ν2
bands only the antisymmetric transitions have been
measured.
In the ν4 band, the smallest transition dipole moments
squared are obtained for the PQ branch. The largest ones
are found for the RP lines with K¼0.
As expected these moments are larger for the ν2 band
compared to the ν4 and 2ν2 bands. Obviously the 2ν2
overtone has the smallest line intensities and transition
moments.
On the other hand, Table 2 and supplementary data
seem to decrease with J for all the branches except for PP,
R
P and RQ branches of the ν4 band. For these branches R2
values increase with J for a given K. This trend can be seen
in Fig. 7 where the R2 values of some manifolds of the RR
branch of the ν4 band are plotted versus J at given K.
As may be seen in Table 2, supplementary data and
Fig. 8, the transition dipole moments squared R2 increases
with K for all branches with exception for PP, PR and Q
10 11 12 13 Fig. 8. Transition dipole moments squared R2(Debye2) for aR(J,K) mani-
Fig. 9. Line mixing effect on pressure dependence of the intensity
P
parameter S for the two components of the asP(3,3) doublet in the ν4
band. The line intensities of the doublet components obtained with
including line mixing effect is smaller than those achieved without
including this effect.
branches of the ν4 and 2ν2 bands respectively. For these
branches R2 values decrease versus K.
5.2. Line-mixing effects on line intensities
For transitions with small rotational energy separation,
or when the gas pressure increases, the lines overlap, and
rotational energy exchanges can mix these lines, transfer-
ring populations between close spectral components and
altering their shapes. In such conditions, because of this
line mixing effect [31,37], the usual Lorentz line profile can
no longer correctly reproduce the experimental spectra.
Then, their rigorous treatment requires accounting for the
line mixing process to obtain accurate spectral line para-
meters. This process is illustrated in Fig. 3a where the
residuals of the spectra are reduced significantly when the
line mixing is taken into account.
The comparison of the measured values of line inten-
sities for the three studied bands exhibits some systematic
behaviors. Within the experimental errors, most of line
intensities in the ν4 band, derived when the line mixing
effect is taken into account, are smaller than those for
which this effect is neglected.
 H. Aroui et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 130 (2013) 273–283
This process is clearly observed in Fig. 9 which illus-
trates the line mixing effect on the pressure dependence of
P
the integrated intensities of the two components of the asP
(3,3) doublet in the ν4 band. From this figure the intensities
of the symmetric (s) component are S0 ¼ 1.35020 70.0181
cm−2 atm−1 and S0 ¼1.85317 0.0326 cm−2 atm−1 respec-
tively obtained with and without including line mixing
effect. For the antisymmetric (a) component the intensities
are S0 ¼1.3322 70.0156 cm−2 atm−1 and S0 ¼1.7641 7
0.0257 cm−2 atm−1 respectively obtained with and with-
out including line mixing effect. This graph also shows that
P
the intensity of the s P(3,3) symmetric line is slightly
P
greater than that of the a P(3,3) antisymmetric one.
The difference between the results obtained with and
without including line mixing (noted by D ¼ ðSWithout −SWith Þ=
SWithout ) is much larger in the ν4 band than in the ν2 and 2ν2
bands. It can be explained partially by the smaller splitting Δs
of the inversion doublets in the ν4 band than in the ν2 and 2ν2
ones. These splitting are 285, 36 and 1 cm−1 for 2ν2, ν2 and ν4
bands respectively.
The D values appear to increase with the decreasing of
Δs. For the PP, PQ and PR branches of the ν4 band these
splitting increase with K quantum number for a given
value of J. While for the RP, RQ and RR branches Δs
decreases with K.
However, the splitting Δs could be large enough to contain
lines other than those pertaining to the doublet of interest.
Therefore the frequency separation between these lines
becomes smaller than the doublet splitting. Then, the line
mixing processes can occur, not only within each doublet, but
also between the components of neighboring doublets pro-
vided that the selection rules are valid. In this case the D
values do not illustrate any clear trends with Δs.
Note also that repeatedly the D values can reach large
values, about 30%, for the components of the doublet with
very small splitting. This is often the case for some J¼K lines
of some branches of the ν4 band. The stronger line mixing
effect occurred in the PP and PQ branches with the smallest
splitting. For these branches the average D values is about 7%.
For the PR, RP, RQ and RR branches the average D values are 4,
3, 5 and 3% respectively. The smallest average D value is less
than 1% obtained for R branch of the ν2 band with a large
inversion gap. This value is smaller than the estimated error
(2%) showing the absence of line mixing in this band. This
comment will be more clarified in the next paragraph.
Due to the spin statistics, the K¼0 lines in Table 2 and
supplementary data do not have symmetric or antisymmetric
partners. These lines have no nearby lines to which they can
couple. This explains the very small differences (≤1%) between
line intensities obtained with and without including line
mixing.
The 2ν2 lines which exhibit significant D values, respec-
tively 13 and 6% for the Q and R branches are strongly
influenced by the Coriolis coupling between ν4a and 2ν2s
partial bands centered at 1627.373 and 1597.469 cm−1
respectively.
5.3. Comparison with previous studies
The goal of this paragraph is to identify which bands
are affected by line mixing effect. The present data can be
281
compared with those of Refs. [1,2,10,13,14,17,18,26,38]
concerning line intensities and transition dipole moments
squared. All these works were performed in the ν2, 2ν2 and
ν4 without considering line mixing effect.
To better analyze these comparisons we define the
relative difference between the data S0PW and S0Oth
obtained in the present work and by the precedent
authors respectively:
D′ ¼ 〈ðS0Oth −S0 PW Þ=S0Oth 〉:
The S0PW values in the ν4 band are compared with the
Cottaz et al. [1] data which are included in the HITRAN
database [8]. For more than 300 transitions with the same
J and K quantum numbers studied in common, the line
intensities predicted by these authors are systematically
greater than ours with a D′ value of about 6% larger than
the measured errors (3%). Note that the Cottaz et al. [1]
predictions are performed using a large set of experimen-
tal line intensities based on Voigt profile.
For the 2ν2 band, the D′ value is also around 6% when
comparison is occurred with Ref. [1]. This relatively large
value is not expected since this band has a large splitting
∼235 cm−1; then the line mixing effect, which occurs
essentially between the symmetric and asymmetric part-
ners of the doublets, should be negligible. This is probably
due to the strong Coriolis coupling interactions of this
band with the ν4a partial band.
On the other hand, within the experimental error, our
transition dipole moments squared in the ν2 band are, for
the 37 transitions studied in common in the R branch,
slightly smaller than those obtained by Fabian and Yamada
[14]. On average the difference between the two results is
about 3%.
When comparing our ν2 line intensities with those
reported in the HITRAN data base [8], a mean difference
of about +13% is found. Note that these HITRAN line
intensities result from calculations performed by Kleiner
et al. [38]. This large discrepancy had been underlined by
Guinet et al. [26]. Because the line intensity parameters are
crucial for atmospheric concentration measurements, we
join these authors to recommend an improvement of the
ν2 line intensities in the HITRAN database.
The comparison between the ν2 band results and the
experimental values reported in the same band by
Nemtchinov et al. [2], using a Fourier transform spectra,
does not show any clear trends. Among 36 transitions
studied in common in the R branch, half of them have
intensities 5% smaller than those of these authors. The rest
of them have intensity values 7% greater. Note that the
scatter of these measurements is much greater than the
present experimental error (2%).
We also compared our line intensities with the results
of Ref. [13] in the ν2 band limited to low J values. Among
the 12 lines studied in common, 8 of them have intensities
about 10% greater than ours. For these 12 lines, the values
of Ref. [13] are about 12% systematically greater than those
of Ref. [2]. It should be noted that the Ref. [13] data,
were determined from spectra with a medium resolution
(0.06 cm−1).
Within the estimated errors, the comparison with the
recent measurements of Guinet et al. [26] in the ν2 band,
282 H. Aroui et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 130 (2013) 273–283

illustrates a good agreement with the present data for the work. For the other works the slopes are 0.998 70.042,
21 lines studied in common in the R branch. The D′ value, 0.81070.015 and 0.855 70.017 for the data of Refs.
about 2%, is in the same order of magnitude as the [2,17,18] respectively.
estimated errors in Ref. [26] (1.7%) and in the present
work (2%). This is the more favorable comparison when
5.4. Rotation–vibration interaction
the other experimental results are considered.
Comparison with the JPL database [10] has been done
As mentioned above the largest differences between the
at T ¼295 K after conversion of line intensities in the ν2
two sets of line intensities and transition dipole moments
band from JPL unit to the cm−2 atm−1 unit. The average
squared obtained with and without including line mixing
difference is about 3% for 54 among 73 lines studied in
effect are for the 2ν2 overtone.
common. A discrepancy of more than 10% is observed for
In addition these moments show significant rotational
the other lines.
dependencies. Generally they are mainly caused by the
Also, the present line intensities in the ν2 and ν4 bands
vibration–rotation interactions. Then the transition dipole
can be compared with those obtained in our previous
moments squared R2 can be expressed as a product of
papers [17,18] which omitted line mixing. For the ν2 band
rotational and vibrational parts [22]:
[17], 57 line intensities stated with an experimental error
of about 3%, are compared to the present intensities for R2 ¼ jRv0 j2 f ΔJ;ΔK ðJ; KÞ; ð4Þ
transitions with the same quantum numbers. The D′ value
where Rv0 is the vibrational transition moment and
is about 3% in the same order of magnitude as the two
f ΔJ;ΔK ðJ; KÞ is a correction function analogous to the Her-
estimated errors.
man–Wallis factor describing the rotational dependencies
Since all these previous work [1,2,10,13,14,17,18,26,38]
of R2. For the symmetric top molecules, this function is
have been performed without taking into account line
often represented by a J and K polynomial equation.
mixing, and considering the various experimental errors
Otherwise, in our previous study [18], using Eq. (3), we
and the precedent analysis, one can emphasize that the
have shown that the intensity correction parameters of ν4a
line mixing effect on line intensities data is negligible in
vibrational levels are significantly larger than those for the
the ν2 band. This is expected because in this band the
ν4s levels. This difference is obviously a consequence of the
splitting can attain 36 cm−1. Thus the inversion contribu-
resonance Coriolis coupling interactions between ν4a and
tion to the line mixing should be smaller compared to that
2ν2s vibrational states that is missing in the case of the
of the ν3 and ν4 bands with very small inversion splitting.
opposite parities.
For the ν4 band, line intensities of 58 lines pertaining to
Here the evaluation of these parameters is rather
the PP branch are compared with those of Ref. [18]
complicated since the Aliev work [22], used in Ref. [18],
measured using the method of absorbance at the line
gives a polynomial equation for each branch of a consid-
center with an estimated error of about 5%. The D′ value is
ered band. Thus for each band, one can get as many
about 10% illustrating a significant line mixing effect
intensity parameters as branches. This is not realistic;
within the inversion doublets of this band.
therefore the use of a more sophisticated theoretical
Finally to more quantify the above analysis, we have
model is needed to derive the intensity parameters (Rv0 ,
plotted the present line intensities as a function of the
band strengths, Coriolis and l-type constants, Herman–
results of Refs. [1,2,17,18]. Fig. 10 illustrates a sample plot
Wallis correction parameters). The present line intensities
for the PP branch of the ν4 band as a function of those in
obtained with taking into account line mixing, are thus of
Ref. [1]. The slope of fit line, equal to 0.946 70.004, shows
great interest to determine with good accuracy these
clearly the line mixing effect taken into account in this
parameters.

1.4 6. Conclusion

1.2
PW line intensity (cm-2 atm-1)

In the present study we have obtained absolute line

1.0 intensities for nine branches in the ν4, 2ν2 and ν2 bands of
NH3 for about 462 lines with J≤12. The accuracies of the
0.8 measurements are estimated to be 2%, 4% and 3% for the
ν2, 2ν2 and ν4 bands respectively
0.6
The analyses of recorded spectra were made with and
0.4 without taking into account line mixing effects. The
differences between the two results can attain 7% depend-
0.2
ing on the rotational quantum numbers, the branch, and
0.0 the band. The larger differences are obtained in the PP and
P
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 Q branches of the ν4 band with small inversion splitting.
Cottaz et al. line intensity (cm-2 atm-1) Measured intensities in the ν2 band agree well with
recent experimental data in Refs. [10,14,17,26,38] obtained
Fig. 10. Present work (PW) line intensities of the PP branch of the ν4 band
as a function of the Cottaz ones [1]. The slope of fit line, equal to
without considering line mixing effect. Then we can
0.946 7 0.004, shows clearly the line mixing effect taken into account in conclude that line mixing effect on line intensities data is
this work. negligible in this band.
 H. Aroui et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 130 (2013) 273–283
Moreover in the ν2 band a large discrepancy (about
10%) is illustrated with respect to values in the HITRAN08
database [8]. Because line intensity parameter is essential
for atmospheric observations, the ν2 band HITRAN data
base requires an improvement.
In the ν4 band, a mean difference of 6% is found when
the present data are compared with those of HITRAN08
database [8]. Thus line mixing effect must be taken into
account for the line intensity analysis in this band.
The determined transition dipole moments squared
illustrate significant rotational dependencies. They are
mainly caused by the Coriolis and l-type interactions
between the ν4 and 2ν2 bands. Then, a sophisticated model
should be used to derive an improved set of intensity
parameters. The whole set of the measured data are given
as supplementary data of the present paper. They are
intended for use in spectroscopic databases.
Acknowledgment
The authors wish to thank Dr. Linda R. Brown (NASA JPL,
Pasadena, USA) for suggesting this study, and Dr. J. Orphal for
his significant contribution in recording of NH3 absorption
spectra.
Appendix A. Supplementary material
Supplementary data associated with this article can be
found in the online version at http://dx.doi.org/10.1016/j.
jqsrt.2013.04.021.
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