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Absorption spectrum of D2O between 10000–11000 cm-1
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Absorption spectrum of D2O between 10000–11000 cm-1 Viktor I. Serdyukov, Leonid N. Sinitsa, Alexander D. Bykov, Elena R. Polovtseva n, Anatolii P. Scherbakov Institute of Atmospheric Optics, Russian Academy of Sciences, Tomsk, Russia
art ic l e i nf o
a b s t r a c t
Article history: Received 14 January 2017 Received in revised form 10 February 2017 Accepted 10 February 2017
A study of the vibration-rotation absorption spectrum of the D2O molecule in the range 10100–10800 cm-1 has been performed. The spectrum was recorded using a Fourier Transform Spectrometer with the spectral resolution of 0.05 cm-1 coupled to the multi-pass White-type cell providing an optical path length of 24 m. A light-emitting diode was used as the radiation source, giving a high brightness that resulted in an S/N ratio of measurements of about 104. The rovibrational assignment of more than 920 lines was carried out, and the parameters of the spectral lines (i.e. centers, intensity and half-width) were determined by leastsquares fitting of the Voigt contour parameters to the experimental data. A total of 530 rotational energy levels belonging to nine vibrational states (301), (103), (400), (221), (122), (320), (004), (023) and (042) and with maximum rotational quantum numbers J¼16 and Ka¼9 was determined. 101 energy levels were derived from the experiment for the first time. & 2017 Published by Elsevier Ltd.
Keywords: Fourier transform spectroscopy LED sources D2O absorption spectrum Vibration-rotation energy levels
1. Introduction The absorption spectra of deuterated isotopic variants of the water molecule (HDO and D2O), are of great interest, as they play an important role in many scientific and technical problems. In this regard, studies of the dynamics of molecular vibrations and rotations, reconstruction of the intramolecular potential energy function from experimental data, studies of intermolecular interactions, and investigations of the role of deuterium in interstellar space and in the atmosphere of planets, are all important. From a practical viewpoint, the absorption spectra of water isotopologues are used as an indicator of chemical reactions in the study of industrial pollution, in laser technology, etc. The D2O molecule has been the subject of extensive spectroscopic investigations in the microwave, and particularly in the infrared range, over the last 40–50 years. There is a large number of studies of the D2O absorption spectra [1–11]. A critical analysis of these studies contains a detailed description of the research of heavy water spectra [5]. Measurements of absorption spectra in the region between 10200–10440 cm-1 have been performed [3] using an IFS-125HR-Fourier spectrometer with a spectral resolution of 0.04 cm-1, and a multi-pass cell providing an optical path length of 105 m. The D2O gas sample pressure was 2352 Pa. The lines attributed to the 3ν1 þ ν3 band were recorded and assignment was performed for lines corresponding to total angular momentum quantum number up to J¼ 13. The experimental n
Corresponding author. E-mail address: [email protected] (E.R. Polovtseva).
spectrum [3] contains 194 transitions, while there are data only for the line centers, and no data on line intensities. The D2O absorption spectrum recorded by the Reims-Brussels collaboration with Fourier Transform Spectroscopy between 10000– 13200 cm-1 with 600 m path length at a resolution 0.03 cm-1 was presented in [10]. The spectrum was analyzed, and the set of 436 experimental energy levels was derived for 10 vibrational states. Also, the D216O absorption spectra in the ranges of 9160–9390 cm-1, 12450–12850 cm-1, 11400–11900 cm-1 and 13600–14020 cm-1 were investigated with high sensitivity by intracavity spectroscopy techniques [2,4,8,11]. Measurements of molecular absorption spectra in the visible region using a Fourier Transform spectrometer are complicated by many factors. The main problem is the low intensity of the molecular absorption lines, which requires the use of long multipath cells to provide a sufficiently long optical path length for the detection of weak lines. To use such cells, it is necessary to use mirrors with high reflection coefficient, because this determines the optimal absorption path [12]. Commonly used broadband mirrors coated with gold are effective in the infrared region: their reflectance coefficient reaches 99%. However, their use is impractical in the visible range; the reflectance falls to 80% or less. The intensity of the radiation passing through the cell can be significantly increased by using narrow-band mirrors with dielectric coatings. Such mirrors reflect up to 99.99% of the radiation, but have a narrow spectral range. In this regard, for the visible range, the most promising mirrors are broadband silver mirrors coated with a protective layer to ensure the reflection coefficient R to be 96–98%.
http://dx.doi.org/10.1016/j.jqsrt.2017.02.009 0022-4073/& 2017 Published by Elsevier Ltd.
Please cite this article as: Serdyukov VI, et al. Absorption spectrum of D2O between 10000–11000 cm-1. J Quant Spectrosc Radiat Transfer (2017), http://dx.doi.org/10.1016/j.jqsrt.2017.02.009i
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In this study, we aim to research the D216O molecule absorption spectrum in the range of 10100–10800 cm-1 using Fourier Transform techniques with light emitting diode (FT-LED). The high spectral brightness of the LED, two orders of magnitude exceeding the brightness of halogen lamps in this spectral region, provides a sufficiently high signal to noise ratio (S/N) to record weak absorption. Our results (i.e. the measured line centers and line intensities) were compared to calculated values [6] and to the results of previous measurements [3,10].
2. Experiment The absorption spectra of Н2О, HDO and D2O in the range 10100– 10800 cm –1 were recorded using a IFS-125M Fourier transform spectrometer with a spectral resolution of 0.05 cm–1 and optical path length of 24 m. A cell with base length of 60 cm and a multipass White optical scheme was used. The multipass cell uses wide-band mirrors with silver-coated protective layers of SiO2 and Al2O3 having a reflection coefficients RE98%. The measurements were performed in a temperature-stabilized room at a fixed temperature of 29771 K. The small length of the cell makes it easier to maintain a stable temperature over the entire optical path. As a radiation source, we used a EDEI-1LS3-R light-emitting diode with a high spectral brightness in the region of 0.9 μm (with a maximum in the 10370– 10670 cm-1 spectral range), which allowed us to obtain a signal-tonoise ratio of about 104 and to detect weak absorption lines with intensities on the order of 10–27 cm/molecule. To achieve a high signal-to-noise ratio, the measurements were performed over several days, and the spectrum was obtained by averaging over 8960 scans. The measurement technique with the use of light-emitting diodes is described in more detail in [12,13]. Some conditions of the present measurements are shown in Table 1. The line parameters were determined with the Wxspe software package, which is able to perform an automatic search of peaks using methods of pattern recognition theory [16]. This package allows one not only to find the peaks in the spectrum, but also to fit the contour parameters (the Voigt contour in our case) to the measured dataset by the least-squares method using the Tikhonov regularization procedure. For each parameter of the contour, its center, halfwidth, and intensity, we determined confidence intervals. For groups of overlapping lines, the parameters of all lines were fitted simultaneously. This fitting was performed taking into account the triangular instrumental function with a HWHM of 0.05 cm–1. The ambiguity in the determination of the center of isolated lines does not exceed 0.008 cm-1, and their intensity: 12%. For some weak lines for which the noise level was comparable to the signal, the centers and intensities were determined from the absorption at the line peaks. The intensities of the lines were compared with the line intensities calculated in [7] using a highly accurate ab initio dipole moment function. The analysis of the spectra in the range considered revealed more than 920 lines with intensities from 8 10–28 to 6.4 10–24 cm/molecule.
In this study, the absorption spectra of three samples were recorded: 1) mixture of H2O, D2O and HDO (at a ratio of H2O and D2O of 50:50); 2) the sample with high D2O concentration (“pure D2O”) and 3) the spectrum of water vapor with natural abundance of isotopic variants (“pure H2O”). All measurements were performed at a pressure of 27 mbar. Fig. 1 shows a transmission spectrum measured in the range under study. Note that the minimal transmission in this spectral range is T¼ 0.990; the inset shows the spectrum in a narrow range containing only very weak lines with transmission on the order of T¼ 0.9997. One can see that weak absorption lines that correspond to absorption coefficient 10-6–10-7 cm-1 are well defined by the Fourier spectrometer used in our work. Calibration of the spectrum was performed using the well isolated strong lines of the H2O molecule, which were observed in the spectrum of the gas mixture. The data of the International Union of Pure and Applied Chemistry (IUPAC) project [14] were used in our work as secondary frequency standards, since the energy levels and the centers of the Н2О lines presented there are the most precise to date. The calibration coefficient was determined by the least-squares method, which is equal to 1.000001001. The partial pressures of components of the samples are determined by using the intensities of the strongest lines of the H2O and HDO UPAC data [14,15]. The values of the partial pressures are given in Table 2. At the pressures indicated in Table 2, the intensity of the strongest line in D216O in samples 2 and 3 are the same within the measurement accuracy of 12%.
3. Results and discussion The D2O absorption spectrum in this work was investigated in the spectral range 10000–11000 cm-1. The D2O absorption spectrum in the region of 10100–10453 cm-1 is formed by transitions to the vibrational states (400), (301), (221), (122), (023), (320), (042). The D2O spectral lines in the spectral region from 10600–11000 cm-1 mainly belong to the ν1 þ3ν3 band; weak transitions of the 4ν3 band in this spectral region were observed. Line assignments in the
Table 1 Measurement conditions at 0.97 μm. Spectral resolution 0.05 cm-1 Diaphragm 1.4 mm Apodization triangle Optical path length 2400 cm Temperature 2977 1 K Scan number 8960 LED EDEI-1LS3-R Duration of measurements 12 days Pressure of mixture H2O, D2O и HDO 27 mBar Beamsplitter quartz
Fig. 1. D216O Transmission spectrum in the region 10000–11400 cm-1.
Table 2 Partial pressures of H2O, HDO and D2O in mixtures. N 1 2 3
Sample Mixture Pure D2O Pure H2O
Molecules H2OþHD D216O H2O
16
OþD216O
HDO
D216O
H2O
14 5 0
6 24 0
7 0.6 27
Please cite this article as: Serdyukov VI, et al. Absorption spectrum of D2O between 10000–11000 cm-1. J Quant Spectrosc Radiat Transfer (2017), http://dx.doi.org/10.1016/j.jqsrt.2017.02.009i
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Table 3 Statistic of the observed transitions of the D216O molecule. Band
Spectral region, cm-1
Number of assignments
Jmax.
Kamax.
Intensity
ν1 þ 3ν3 3ν1 þ ν3 4ν1 ν1 þ 2ν2 þ23 3ν1 þ 2ν2 4ν3 2ν2 þ 3ν3 4ν2 þ 2ν3 2ν1 þ 2ν2 þν3
10486–10915 10076–10482 10125–10790 10068–10442 10081–10258 10787–10970 10147–10760 10170–10445 10018–10410
175 333 88 37 21 31 7 4 224
14 16 13 14 10 12 12 11 14
7 9 7 7 5 6 5 5 8
4.6*10–24 6.4*10–24 7.9*10–25 6.9*10–25 1.8*10–25 2.9*10–26 4.7*10–25 1.1*10–25 1.2*10–24
Fig. 2. Comparison of the experimental and calculated [6] line intensities in the 10600–10800 cm-1 spectral region. Intensity ratio as a function of observed line intensity.
Fig. 3. Differences (cm-1) between experimental and calculated [6] D216O line positions in the 10100–10453 см 1 spectral region.
spectrum was carried out using the results of the large-scale variational calculations [6], based on high quality potential energy surface. The centers of lines of [6] are the best at the moment. The line list of [6] was supplemented with intensities of lines from [7], which were calculated with highly accurate vibrational-rotational wave functions and an ab initio dipole moment function of D2О. The typical error of these calculated intensities for strong lines is 5–10%. As a result of the spectrum analysis, the experimental line list was obtained, including 926 transitions to ten vibration states. All transitions are from the (000) ground vibrational state to the upper vibrational states and only one weak transition is from the (010) state to the (311) state. Statistics of the observed transitions of the D2O molecule are shown in Table 3. Table 3 gives the spectral range, a number of identified lines, the maximum value of the rotational quantum numbers J and Ka, and the maximum and minimum line intensities for bands. Table 3
max.
cm/molecule
Intensity
min.
cm/molecule
1.1*10–27 3.3*10–27 1.7*10–27 5.6*10–27 6.8*10–27 9.3*10–28 9.2*10–27 1.5*10–26 9.5*10–28
shows that the strongest bands are ν1 þ3ν3 in the region of 10600– 10800 cm-1, and 3ν1 þ ν3 in the region of 10134–10450 cm-1. A comparison of experimental intensities for lines between 10600– 10800 cm-1, where the band ν1 þ 3ν3 is situated, with the calculated intensities of [6], is shown in Fig. 2. In this study, 334 transitions belonging to the 3ν1 þ ν3 band and 89 transitions of the 4ν1 band were assigned; while in [3] 184 transitions of the 3ν1 þ ν3 band and 10 transitions of the 4ν1 band were obtained. In addition, in [3] the data on the line intensities have not been reported, only line positions are given. In this study we present a line centers, as well as their intensity. The largest deviations are observed for those D2O lines that overlap with the HDO lines; in this case, distortion of the D2O lines intensities takes place. A comparison of the intensities shows their general agreement within 15–20%. For the lines of the strongest bands ν1 þ3ν3 with an intensity higher than 5 10–25 cm/molecule, the average ratio of the experimental intensities to the calculated values is 1.1 70.07. The standard deviation of the measured lines centers from the calculated ones [6] in the region amounted to 0.036 cm-1. Fig. 3 shows a comparison of the experimental and calculated line centers for the region 10100–10453 cm-1. This figure shows that the experimental line centers are in good agreement with the calculations [6]. The maximum deviation experimental line centers to the calculated data [6] are 0.02 cm-1. The average ratio of the experimental intensities of the strongest lines in the region 10100–10453 cm-1 to the intensities calculated in [6] is 1.03 70.07. Thus, we can conclude that our measured data agree well with the data of [3] within the measurement error, and confirm the ab initio calculations of [6]. To validate the correctness of the interpretation of lines and energy levels determination, we used the software package SLON [17], which uses the Rydberg-Ritz combination principle and allows the line in automatic mode to be interpreted. This package performs line assignment by extensive use of pattern recognition methods, and uses the calculated values of the line centers and the line intensities as input data. The energy levels of the upper states were obtained by adding the center lines of a transition to the energies of the lower rotational state, and averaging over all the transitions to the same upper state. For 312 energy levels, the proposed interpretation is confirmed by the combination rule, while for other levels our assignments are confirmed by good match between observed and calculated intensities, (see Fig. 2) and regularity in the obs.- calc. differences for line positions within a bands (see Fig. 3). As a result of the spectrum analysis in the range of 10000–11000 cm-1, 530 ro-vibrational energy levels were derived, including 151 rotational sublevels of the (301) vibrational state, 106 levels of the (103) state, 67 levels of (400) state, 114 levels of (221) state, 32 levels of (122) state, 31 levels of (004) state, 20 levels of (320) state, 7 levels of (023) state and one level of the highly excited bending (042) state. All these levels correspond to rotational quantum numbers Jr 16 and Ka r9.
Please cite this article as: Serdyukov VI, et al. Absorption spectrum of D2O between 10000–11000 cm-1. J Quant Spectrosc Radiat Transfer (2017), http://dx.doi.org/10.1016/j.jqsrt.2017.02.009i
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Table 4 D216O rovibrational energy levels of the (301), (400), (221), (103), (122),(320),(004), (023) and (042) vibrational states between 10000 and 11000 cm-1. J
Ka
Kc
(301) Eobs.
N
s
0 1 1 1 2 2 2 2 2 3 3 3 3 3 3 3 4 4 4 4 4 4 4 4 4 5 5 5 5 5 5 5 5
0 0 1 1 0 1 1 2 2 0 1 1 2 2 3 3 0 1 1 2 2 3 3 4 4 0 1 1 2 2 3 3 4
0 1 1 0 2 2 1 1 0 3 3 2 2 1 1 0 4 4 3 3 2 2 1 1 0 5 5 4 4 3 3 2 2
10358.5619 10370.2111 10377.3146 10379.7253 10392.9494 10397.8479 10404.2259 10426.7597 10427.2730 10425.8247 10428.6198 10443.5548 10461.1619 10463.5796 10503.3932 10503.4671 10468.0129 10469.3465 10495.9234 10506.7007 10513.1127 10550.1421 10550.6261 10607.6506 10607.6507 10519.1590 10519.7118 10555.5684 10563.1266 10575.7512 10608.6490 10610.4455 10666.1861
1 3 2 2 3 3 3 2 2 4 3 3 2 3 2 2 4 4 3 4 3 3 3 2 2 3 2 3 3 3 3 2 3
1.97 0.79 0.43 5.37 0.69 1.38 0.13 0.16 3.03 4.87 0.16 3.47 0.18 2.72 0.24 6.49 4.93 2.68 0.87 2.56 2.66 0.95 3.82 2.03 5.00 0.87 3.79 4.09 0.58 2.26 0.56 2.57
5 5 5 6 6 6 6 6 6 6 6 6 6 6 6 6 7 7
4 5 5 0 1 1 2 2 3 3 4 4 5 5 6 6 0 1
1 1 0 6 6 5 5 4 4 3 3 2 2 1 1 0 7 7
10666.2579 10739.3098 10739.3123 10579.2685 10579.4652 10625.8671 10630.1705 10650.6969 10678.7626 10683.5620 10736.6726 10737.0090 10809.5268 10809.5213 10898.1295 10898.1297 10648.4201 10648.4612
3 2 2 3 3 3 5 4 5 4 3 3 3 2 2 2 3 2
1.44 3.09 0.03 2.23 2.01 5.56 5.78 4.86 5.60 2.32 4.24 1.90 4.50 1.03 0.94 1.13 1.75 2.27
7 7 7
1 2 2
6 6 5
7 7 7
3 3 4
5 4 4
10705.5322 10707.4834 10736.5837 I 10747.6000 II 10760.2331 10770.3078 10819.1184
4 4 3 3 3 3 3
10.34 9.30 0.29 5.03 0.98 2.14 0.90
7 7 7 7 7 7 7 8 8 8 8 8 8
4 5 5 6 6 7 7 0 1 1 2 2 3
3 3 2 2 1 1 0 8 8 7 7 6 6
10820.2727 10891.7115 10891.8693 10980.0880 10980.0893 11084.2851 11084.2854 10726.6586 10726.6736 10794.0366 10794.7074 10843.7679 10852.8066
3 3 3 3 3 1 1 2 2 2 5 2 3
2.62 6.66 6.89 8.09 7.12
0.28 1.70 0.86 4.22 3.36 12.73
(400) Eobs.
N
10341.0132 10352.6152 10360.1766
1 1 1
s
10380.9054
1
10408.2630 10411.7456 10426.6153 10439.6107 10443.0257 10485.0885 10485.0883 10450.5841 10452.4665 10476.9498 10485.8808 10493.1300 10532.5808
2 1 1 2 1 2 1 2 1 2 2 1 1
10590.7462 10590.7460 10501.8850 10502.7775
2 2 1 2
3.59 3.90
10542.8999
3
2.77
10592.0468 10593.0954 10650.0270 10846.3849II 10650.0256 I 10723.7010 10723.6990 10562.0853 10562.5118
2 2 2 1 1 2 1 1 1
8.42 0.08 4.31
10610.3327
1
10663.6687 10666.4372 10721.2964 10721.4965 10794.7347 10794.7238 10883.8150 10883.8206 10631.3268 10631.4836 I 10828.6712 II
2 2 1 2 1 2 1 1 1 2 1
10753.2860 10804.6101I 11000.5329II
1 2 1
10877.7070 10877.6229 10966.6711 10966.7051
1 1 1 1
10774.9375
1
11.40
1.36 5.59 7.75 12.09 2.94
1.03
1.99
0.63 7.39 0.37 10.59
4.03
5.5
(221) Eobs.
N
s
(103) Eobs.
N
s
10180.1181 10191.9086 10201.4125 10204.0974 10215.0008 10222.6544 10230.4688 10258.7489 10259.2233 10248.4628 10251.4518 10269.5445 10293.5689 10295.8196 10347.8325 10347.8832 10291.3988 10293.6301 10320.8031 10339.7720 10345.6748 10395.3221 10395.7116 10468.6875 10468.7389 10343.2671 10344.4605 10383.4639 10397.1684 10408.3943 10454.7953 10456.2770 10528.1335
1 2 2 2 2 3 3 2 2 3 2 3 3 3 2 2 2 3 2 4 3 3 3 2 2 3 2 3 3 3 3 3 3
3.05 2.04 0.50 12.53 1.07 3.82 3.89 6.88 7.72 4.37 1.41 4.72 5.79 1.04 0.06 2.28 0.58 0.75 1.00 9.63 6.08 7.21 6.39 6.65 4.58 4.17 2.14 2.48 4.24 5.65 3.32 2.53
10691.3838
2
0.99
10700.5574 10714.2121 10719.0481 10726.4286 10746.4973 10747.0597 10747.2349 10750.1432 10764.8029 10781.6355 10784.2743 10821.3309 10821.4426 10789.5938 10791.1196 10815.0704 10828.0593 10835.0276 10869.1718 10869.7558 10922.9521 10922.9464 10840.9744 10841.6010 10876.3214 10885.2636 10899.1630 10928.9738 10931.0418 10983.0619
2 2 3 2 2 2 2 2 2 1 2 2 1 2 1 2 1 2 3 2 1 1 2 2 2 3 4 1 3 2
0.60 14.16 1.84 1.48 0.52 3.92 1.57 1.53 2.18
10528.2824 10620.6017 10620.6053 10403.9644 10404.5140 10456.5323 10465.4717 10493.2646 10526.1349 10530.1845 10599.5767 10600.0688 10691.9221 10691.9119 10802.1550 10802.1551 10473.5631 10473.8031
3 2 1 2 3 1 3 2 3 2 3 2 2 2 2 2 2 2
2.36 4.02 1.33 7.93 2.71 3.62 6.42 10.86 23.30 23.10 0.08 4.56
10983.1489 11051.1402 11051.1428 10901.3783 10901.6124 10947.5022 10952.9353 10975.9938 11000.5283 11005.9527 11055.3494 11055.7552 11123.6460 11123.6374 11205.4303 11205.4302 10970.9655 10970.9412
3 2 2 3 2 1 2 3 4 2 4 2 2 1 1 1 2 1
10538.9852 10544.2591 10582.1682
1 3 3
2.10 2.37
11027.8679 11030.6568 11064.2597
3 2 1
2.76 1.84
10609.0607 10617.9188 10682.6370
2 3 3
1.99 3.74 1.80
11083.4536 11094.7560 11139.7618
2 2 1
2.59 7.82
10684.3855 10775.3837 10775.4264 10885.0497 10885.1649 11011.3393 11011.3395 10551.9685 10552.2393 10630.1889 10633.0365
3 2 3 1 1 1 1 2 1 2 2
2.25 0.05 3.98
11141.1124
3
3.27
11208.1726 11291.1322 11291.1318
2 1 1
6.67
2 2 1 3
15.93 2.99
1.68 4.12
11049.9985 11049.6205 11117.2190 11118.1198
2.63
10704.6844
3
6.74
11177.3113
2
13.94
0.43 4.16 0.34 8.41
1.2
1.72 16.15 0.76 0.43 8.46 3.18 20.20
6.31 7.28 1.88 2.49 3.17 5.06 6.05 7.80 0.34 2.77 6.22 3.33 2.22 6.58 5.12 3.01 2.58 5.27 2.98
2.38
Please cite this article as: Serdyukov VI, et al. Absorption spectrum of D2O between 10000–11000 cm-1. J Quant Spectrosc Radiat Transfer (2017), http://dx.doi.org/10.1016/j.jqsrt.2017.02.009i
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Table 4 (continued ) J
Ka
Kc
(301) Eobs.
N
s
(400) Eobs.
N
8 8 8 8
3 4 4 5
5 5 4 4
10869.8842 10913.4471 10916.6484 10985.8746
4 3 3 3
6.90 3.50 2.83 0.97
10853.6366 10899.8450
1 1
10972.6252I 11170.8019II
1 1
8 8 8 8 8 8 8 9 9 9 9 9 9
5 6 6 7 7 8 8 0 1 1 2 2 3
3 3 2 2 1 1 0 9 9 8 8 7 7
10986.1740 11073.9605 11073.9585 11178.2612 11178.2613 11300.0240 11300.0242 10814.0108 10814.0467 10891.3976 10891.4929 10951.1104 10956.1154
2 2 2 2 2 2 2 2 2 3 3 3 4
8.97 4.43 6.75 1.48 1.82 1.92 2.09 7.87 3.88 1.51 3.48 6.13 4.90
9 9 9 9
3 4 4 5
6 6 5 5
10983.7555 11019.4671 11026.5653 11092.0615
3 2 2 2
3.82 0.95 0.62 2.76
9 9 9 9 9 10 10 10 10 10 10 10 10
5 6 6 7 7 0 1 1 2 2 3 3 4
4 4 3 3 2 10 10 9 9 8 8 7 7
11092.8887 11179.8778 11179.8612 11283.6254 11283.6250 10910.4559 10910.4698 10997.8541 10997.6192 11066.2032 11068.7796 11107.8982 11136.8653
3 2 2 1 1 3 2 2 2 2 2 2 3
3.61 13.92 7.00
10 10 10 10 10 10 10 10 11 11 11 11 11 11 11 11 11 11 11
4 5 5 6 6 7 7 8 0 1 1 2 2 3 3 4 4 5 5
6 6 5 5 4 4 3 3 11 11 10 10 9 9 8 8 7 6 7
11150.3560 11210.2784 11212.3149 11298.1404 11297.8190
2 3 2 2 2
6.69 4.08 9.03 13.88 0.70
11 11 11 11 11 12 12 12 12 12 12 12 12 12 12 12 13
6 6 8 9 9 0 1 2 2 3 3 4 4 5 5 6 0
6 5 4 3 2 12 12 11 10 10 9 9 8 8 7 6 13
3.82 2.28 11.43 3.54 2.54 0.26 0.55 9.41
11016.0431 11016.0575 11112.8757 11113.1123 11191.9067 11191.4273 11256.5491 11265.2727
2 2 2 1 1 2 2 2
0.67 9.11 6.20
11344.9423 11340.3577
3 1
2.82
11428.6921 11428.0074
2 1
14.63
11754.2461 11754.2460 11130.7226 11130.7161 11238.0996 11326.9691 11327.1365
1 1 2 2 2 1 1
11403.8892 11437.6745 11481.8792 11491.3306
1 1 1 2
11254.5479
1
0.54 0.13 1.45
11061.4691 11165.2287
1 1
10936.8055 I 11142.1170 II
2 1
1.33
11007.0118 11011.6073 11079.4788I 11280.3823II
3 1 1 1
6.55
11272.9023
2
10893.1230 10893.0677
1 1
11248.4592
II
1 1
11383.3374
1
II
10998.5352 10998.6075
11241.9018
(221) Eobs.
N
s
(103) Eobs.
N
s
10719.4718 10778.1048 10781.6413 10871.0986
2 1 3 2
0.95 6.97 4.92
11197.0446 11236.1568 11239.9567 11305.1193
2 2 3 3
0.73 7.21 4.62 6.82
10871.7432 10980.2630 10980.2444 11105.4192 11105.4189
2 2 1 1 1
2.50 6.60
11388.9144
1
11487.0942 11487.0940
1 1
10639.6552 10639.7419 10729.9577 10731.4305 10798.6874 10809.9513
1 2 2 1 3 2
11134.4151 11138.3840 11216.1921 11215.2083
2 1 1 2
11281.5582
1
10834.0296 10889.7952 10892.3416 10979.1803
1 2 2 2
4.37 22.12 6.15
11311.9706 11344.2274 11352.2929
2 2 3
10978.7346 11087.5471
3 2
6.37 24.86
10736.2878 10736.3209 10838.3790 10838.7695
2 2 2 1
18.19 4.12 6.05
11233.5556 11232.7211
1 1
10926.2694
2
7.45
11395.8726
1
11008.3954
1
11463.4999
2
3.10
11016.8363
1
11478.5664 11534.9474
3 2
12.79 1.71
11099.4021 11207.0468 11206.9663 11330.3005 11330.3049 11525.6437 10841.9118 10841.9359 10955.6069
1 3 1 2 2 1 1 1 1
11339.3712 11339.2158
1 1
11518.7254 11574.3849
1 3
11673.0014
1
11454.5727 11454.5751
1 1
11718.8324
1
11770.3160
2
7.07
11578.9010
2
4.10
8.05 0.15 2.87 2.54
2.38
19.20
0.45 8.52 3.22
1.70
1
11125.9835I 11327.6299II
11509.6944I 11534.1823II
7.33 1.51 5.33
s
1 1
1
5.27 22.12 15.45
4.58
0.62 11154.9735 11232.8630
1 1
11657.5231
1
10957.2200
1
11186.2286
1
1
19.24 11482.6561
1
Please cite this article as: Serdyukov VI, et al. Absorption spectrum of D2O between 10000–11000 cm-1. J Quant Spectrosc Radiat Transfer (2017), http://dx.doi.org/10.1016/j.jqsrt.2017.02.009i
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Table 4 (continued ) J
Ka
Kc
(301) Eobs.
N
s
13 13 13 13 13 13 13 14 14 14 14 14 14 14 14 15 15 15 15 16 16
1 1 2 2 3 3 5 0 1 1 2 3 3 4 5 0 1 1 2 0 0
13 12 12 11 11 10 8 14 14 13 13 12 11 11 10 15 15 14 13 16 16
11254.4569 11371.2146 11371.6528 11470.1495 11469.3629 11558.9212 11651.4012 11387.2090 11387.2091
2 2 1 1 2 1 1 1 1
0.34 0.91
11514.2166 11621.5107
1 2
J
Ka
1 1 2 2 2 3 3 3 3 3 3 4 4 4 4 4 4 4 5 5 5 5 5 5 5 6 6 6 6 6 6 6 6 6 7 7 7 8 8 8 8 8 9 9 9 9 9 9 9 9
0 1 0 2 2 1 1 2 2 3 3 0 1 2 3 3 4 4 1 2 2 3 3 4 5 1 2 2 3 3 4 5 6 6 1 3 5 0 1 2 3 5 1 2 3 4 5 5 7 7
Kc
1 1 2 1 0 3 2 2 1 1 0 4 3 2 2 1 1 0 5 4 3 3 2 2 1 5 5 4 4 3 2 1 1 0 6 5 3 8 7 7 5 3 9 8 7 6 5 4 3 2
11529.0124 11529.0124 11660.0210 11780.7316 11679.8300 11679.8292 (122) Eobs.
2 2 1 1 1 1 N
(400) Eobs.
s
10448.3088 10450.2294 10498.4722
3 1 1
5.97
10500.9602 10546.7445 10547.1498
3 1 1
6.33
10550.9345
4
5.47
10608.6894
1
(023) Eobs.
N
10506.7681
1
10570.4612
10659.9896
1 1
10700.7855 10785.4021 10787.1862
1 3 2
11022.5966 10788.6867 10885.6195
1 1 1
11217.0900
1
s
1 1
s
(320) Eobs.
N
s
(103) Eobs.
N
s
11578.9036 11692.2796
2 1
6.08
11790.6854
1
11984.6323
1
11835.2042 11835.1889
1 1
12037.8888 12051.2344 12143.9948 11854.7500
1 1 1 1
11987.0407
1
(004) Eobs.
N
10879.2852 10895.9338
1 1
10927.4457 10931.7013 10946.5567 10962.2427
1 1 1 1
11000.2422 11000.3383 10971.5943 10997.1184
1 1 1 1
11049.0981 11099.8397 11099.8689 11023.7422 11066.5602 11081.1420 11108.7673
1 1 1 1 1 1 1
11160.3795 11225.4208
1 1
11134.6484 11158.6669 11180.7966 11186.8828 11233.6756 11298.2344 11376.5258 11376.5428
1 1 1 1 1 1 1 2
11264.2355
1
11379.9223
1
11463.4624
1
s
1 10216.5763
1
10255.6833
2
10307.9924
1
10304.7274 10356.5874
1 1
9.04
1
4.95
10743.0309
1
10839.9147
1
10854.3178 10947.6639
1 3
17.54
12.57 0.08
11286.7602 11287.2561 11347.7690 11347.7691
N
0.52 1.24
21.34
10693.4621 10763.5587
(221) Eobs.
11359.9273 11487.4827
3.36
2 1
1 2
s
4.52
10412.7144 10413.1087
10611.2256 10619.6709
N
1 1
16.02
1 1
Please cite this article as: Serdyukov VI, et al. Absorption spectrum of D2O between 10000–11000 cm-1. J Quant Spectrosc Radiat Transfer (2017), http://dx.doi.org/10.1016/j.jqsrt.2017.02.009i
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Table 4 (continued ) J
Ka
Kc
10 10 10 10 10 10 11 11 11 12 13 14
1 2 2 5 7 7 1 2 2 1 2 1
9 9 8 6 4 3 10 10 9 11 12 13
J
Ka
Kc
11
5
7
(122) Eobs.
N
s
10990.0486 10994.2951 11071.3272
1 1 2
9.65
11465.5270 11465.5269 11107.1840 11104.2941
1 1 1 2
11232.9580 11365.3823 11508.1256
2 1 2
8.43
N 4
s 7.72
(042) Eobs. 11189.5411
(023) Eobs.
N
s
(320) Eobs.
N
11069.8773
1
s
(004) Eobs.
N
11748.0733
1
s
13.18 11362.7703 11398.9897
1 1
2.91
Notes: Eobs. is observed upper energy level, J, Ka, Kc - rotational quantum numbers,. N is the number of lines used for the upper energy level determination, s (in10-3 cm-1) denotes the rms-statistical error of the deviation of the levels derived through several transitions. Roman numerals I and II denote the levels having the same set of approximate quantum numbers but should be referred to different states on the base of calculation of Ref [11].
The energy levels obtained here were compared with the experimental energy levels obtained in [10] using a Fourier Transform Spectrometer with a long absorption cell. The standard deviation of our data from data of [10] for the ν1 þ3ν3 band is 0.005 cm-1, for the 2ν1 þ2ν2 þ ν3 band is 0.0015 cm-1, and for the 4ν1 band is 0.012 cm-1. This shows good agreement with our experimental data, and the data obtained in [10]. Thesis [10] is not contain the D2O linelist and only energy levels. In comparison with [10] 101 new energy levels belonging to nine vibrational states were derived in our work, including 31 energy levels of the (004) state and one energy level of the (042) vibrational state, which were not investigated in [10]. The frequencies determined here coincide with those obtained in [3] within the accuracy of measurement, but with the exception of some number of lines caused by transitions to the rotational levels [10 1 9],[11 2 10] and [13 0 13] of the vibrational state (301). For these lines, the differences between our values and those of [3] are 0.122 cm-1, 0.347 cm-1, and 0.161 cm-1, respectively. This large difference is caused by the fact that in [3], the HDO lines were falsely attributed to D2O. These three rotational levels are different to the recommended UIPAC data [5] by more than 0.1 cm-1, which is beyond the scope of experimental error. For these lines, Δ ¼Eexp-EIUPAC is equal 0.122 cm-1, 0.347 cm-1, and 0.161 cm-1, respectively. This is because the wrong energy levels of [3] were transferred to the recommended database of the D216O levels. At the same time, our measured energy levels coincide with the calculated ab initio data [6] within the measurement accuracy: the differences do not exceed 0.023 cm-1. The entire set of energy levels is given in Table 4. The accuracy of the observed energy levels is 0.004 cm-1 on average for levels confirmed by the combination differences. The calculations [6] give in some cases the same quantum numbers for levels with different energy. The vibrational problem for the D2O molecules using the method of effective Hamiltonians was solved in [11], where the mixing coefficients of the wave functions were determined. For the vibrational level 10538.494 cm-1 the mixing coefficients are equal to 0.503 and 0.420 for the states (202) and (400), respectively [11]. In the Table 4 Roman numerals I and II denote the levels having the same set of approximate quantum numbers but should be referred to different states on the base of calculation of [11]. Energy levels marked by Roman numerals II should be assigned to (202) vibrational state with the same rotational quantum numbers (for example, the level (400) [542] at 10846.3849 cm-1). Also, (301) [725] level at 10747.6000 cm-1 can be attributed to (400) [735]
rovibrational state because of strong Coriolis resonance. A line list that contains more than 920 D2O transitions is attached to this paper in the Supplementary Materials. The complete dataset containing all the detected transitions is available at http://wadis.saga.iao.ru.
4. Conclusions Using the LED-based Fourier Transform spectrometer allowed us to measure the line positions and strengths of weak absorption lines of D2O molecules near 0.97 μm. The analysis of the spectrum resulted in spectroscopic line parameters that are in good agreement with the calculated data [6] and experimental data [3,10]. We have determined the rotational energy levels of nine vibrational states: (301), (103), (400), (221), (122), (320), (023), (004) and (042). New 101 energy levels were derived from the experiment. The weak (004) and (042) vibrational states were studied for the first time. New measured line centers, intensities, as well as a set of experimentally derived vibration-rotational energy levels can be used further to clarify the absorption capability of D2O and its internal dynamics.
Acknowledgements This work is partly supported by RFBR (Grants No. 16-43700492 and No.17-03-00437 А). The authors express their gratitude to O.V. Naumenko for useful discussions of the vibration-rotation assignment of the D2O lines and to A.S.Sergeeva and T.V.Kruglova for help in spectra analysis.
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.2017.02.009.
References [1] Mellau G, Mikhailenko SN, Starikova EN, Tashkun SA, Over H, Tyuterev VG. Rotational levels of the (000) and (010) states of D216O from hot emission spectra in the 320–860 cm-1 region. J Mol Spectrosc 2004;224:32–60. [2] Campargue A, Mazzotti F, Baguier S, Polyansky OL, Vasilenko IA, Naumenko OV.
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High sensitivity ICLAS of D2O between 12450 and 12850 cm-1. J Mol Spectrosc 2007;245:89–99. [3] Ulenikov ON, Hu S-M, Bekhtereva ES, Onopenko GA, He S-G, Wang X-H, et al. High-resolution fourier transform spectrum of D2O in the region near 0:97 μm. J Mol Spectrosc 2001;210:18–27. [4] Naumenko OV, Mazzotti F, Leshchishina OM, Tennyson J, Campargue A. Intracavity laser absorption spectroscopy of D2O between 11400 and 11900 cm-1. J Mol Spectrosc 2007;242:1–9. [5] Tennyson J., Bernath, PF., Brown, LR. et al. IUPAC critical evaluation of the rotational–vibrational spectra of water vapor. Part IV. Energy levels and transition wave numbers for D216O, D217O, and D218O. // JQSRT 2014;142: pp. 93-108. [6] Shirin SV, Zobov NF, Polyansky OL. Theoretical linelist of D216O up to 16000 cm-1 with an accuracy close to experimental accuracy. J Quant Spectrosc Radiat Transf 2008;109:549–558. [7] Schwenke DW, Partridge H, Tashkun SA. Schwenke-Partridge linelists (PS–1000) for 6OD, 〈http://spectra.iao.ru/1440x747/ru/mol/bands/sp1/7/〉; 2007. [8] Bykov AD, Lopasov VP, Makushkin YS, Sinitsa LN, Ulenikov ON, Zuev VE. Rotation–vibration spectra of deuterated water vapor in the 9160–9390 cm-1 region. J Mol Spectrosc 1982;94:1–27. [9] Bykov AD, Naumenko OV, Polovtseva ER, Hu S-M, Liu A-W. Fourier transform absorption spectrum of D216O in the 7360–8440 cm-1 spectral region. J Quant Spectrosc Radiat Transf 2010;111:2197–2210. [10] Leshchishina OV. Étude expérimentale et théorique du spectre d’absorption de la vapeur d’eau vers 800 nm et de la bande a1Δg – X 3Σg– de l’oxygène vers
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1.27 micron par spectroscopie d’absorption à très haute sensibilité.Thèse soutenue publiquement le 26.08.2011. Campargue A, Leshchishina OM, Naumenko OV. D216O: ICLAS between 13600 and 14020 cm-1 and normal mode labeling of the vibrational states. J Mol Spectrosc 2009;254:1–9. Serdyukov VI, Sinitsa LN, Vasil’chenko SS. Highly sensitive Fourier transform spectroscopy with LED sources. J Mol Spectrosc 2013;290:13–17. Serdyukov VI, Sinitsa LN. New features of an FT spectrometer using LED sources. J Quant Spectrosc Radiat Transf 2016;177:248–252. Tennyson J, Bernath PF, Brown LR, Campargue A, Császár AG, Daumont L, et al. IUPAC critical evaluation of the rotational– vibrational spectra of water vapor. Part III. Energy levels and transition wavenumbers for H216O. J Quant Spectrosc Radiat Transf 2013;117:29–58. Tennyson J, Bernath PF, Brown LR, et al. IUPAC critical evaluation of the rotational-vibrational spectra of water vapor.Part II Energy Levels Transit Wavenumbers HD16O, HD17O, HD18O //. J Quant Spectrosc Radiat Transf 2010; V.111(№. 15):2160–2184. Kruglova TV, Shcherbakov AP. Automated line search in molecular spectra based on nonparametric statistical methods: regularization in estimating parameters of spectral lines. Opt Spectrosc 2011;111:353–356. Bykov AD, Naumenko OV, Pshenichnikov AM, Sinitsa LN, Shcherbakov AP. An expert system for identification of lines in vibrational-rotational spectra. Opt Spectrosc 2003;94:528–537.
Please cite this article as: Serdyukov VI, et al. Absorption spectrum of D2O between 10000–11000 cm-1. J Quant Spectrosc Radiat Transfer (2017), http://dx.doi.org/10.1016/j.jqsrt.2017.02.009i
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Absorption spectrum of D2O between 10000–11000 cm-1 Viktor I. Serdyukov, Leonid N. Sinitsa, Alexander D. Bykov, Elena R. Polovtseva n, Anatolii P. Scherbakov Institute of Atmospheric Optics, Russian Academy of Sciences, Tomsk, Russia
art ic l e i nf o
a b s t r a c t
Article history: Received 14 January 2017 Received in revised form 10 February 2017 Accepted 10 February 2017
A study of the vibration-rotation absorption spectrum of the D2O molecule in the range 10100–10800 cm-1 has been performed. The spectrum was recorded using a Fourier Transform Spectrometer with the spectral resolution of 0.05 cm-1 coupled to the multi-pass White-type cell providing an optical path length of 24 m. A light-emitting diode was used as the radiation source, giving a high brightness that resulted in an S/N ratio of measurements of about 104. The rovibrational assignment of more than 920 lines was carried out, and the parameters of the spectral lines (i.e. centers, intensity and half-width) were determined by leastsquares fitting of the Voigt contour parameters to the experimental data. A total of 530 rotational energy levels belonging to nine vibrational states (301), (103), (400), (221), (122), (320), (004), (023) and (042) and with maximum rotational quantum numbers J¼16 and Ka¼9 was determined. 101 energy levels were derived from the experiment for the first time. & 2017 Published by Elsevier Ltd.
Keywords: Fourier transform spectroscopy LED sources D2O absorption spectrum Vibration-rotation energy levels
1. Introduction The absorption spectra of deuterated isotopic variants of the water molecule (HDO and D2O), are of great interest, as they play an important role in many scientific and technical problems. In this regard, studies of the dynamics of molecular vibrations and rotations, reconstruction of the intramolecular potential energy function from experimental data, studies of intermolecular interactions, and investigations of the role of deuterium in interstellar space and in the atmosphere of planets, are all important. From a practical viewpoint, the absorption spectra of water isotopologues are used as an indicator of chemical reactions in the study of industrial pollution, in laser technology, etc. The D2O molecule has been the subject of extensive spectroscopic investigations in the microwave, and particularly in the infrared range, over the last 40–50 years. There is a large number of studies of the D2O absorption spectra [1–11]. A critical analysis of these studies contains a detailed description of the research of heavy water spectra [5]. Measurements of absorption spectra in the region between 10200–10440 cm-1 have been performed [3] using an IFS-125HR-Fourier spectrometer with a spectral resolution of 0.04 cm-1, and a multi-pass cell providing an optical path length of 105 m. The D2O gas sample pressure was 2352 Pa. The lines attributed to the 3ν1 þ ν3 band were recorded and assignment was performed for lines corresponding to total angular momentum quantum number up to J¼ 13. The experimental n
Corresponding author. E-mail address: [email protected] (E.R. Polovtseva).
spectrum [3] contains 194 transitions, while there are data only for the line centers, and no data on line intensities. The D2O absorption spectrum recorded by the Reims-Brussels collaboration with Fourier Transform Spectroscopy between 10000– 13200 cm-1 with 600 m path length at a resolution 0.03 cm-1 was presented in [10]. The spectrum was analyzed, and the set of 436 experimental energy levels was derived for 10 vibrational states. Also, the D216O absorption spectra in the ranges of 9160–9390 cm-1, 12450–12850 cm-1, 11400–11900 cm-1 and 13600–14020 cm-1 were investigated with high sensitivity by intracavity spectroscopy techniques [2,4,8,11]. Measurements of molecular absorption spectra in the visible region using a Fourier Transform spectrometer are complicated by many factors. The main problem is the low intensity of the molecular absorption lines, which requires the use of long multipath cells to provide a sufficiently long optical path length for the detection of weak lines. To use such cells, it is necessary to use mirrors with high reflection coefficient, because this determines the optimal absorption path [12]. Commonly used broadband mirrors coated with gold are effective in the infrared region: their reflectance coefficient reaches 99%. However, their use is impractical in the visible range; the reflectance falls to 80% or less. The intensity of the radiation passing through the cell can be significantly increased by using narrow-band mirrors with dielectric coatings. Such mirrors reflect up to 99.99% of the radiation, but have a narrow spectral range. In this regard, for the visible range, the most promising mirrors are broadband silver mirrors coated with a protective layer to ensure the reflection coefficient R to be 96–98%.
http://dx.doi.org/10.1016/j.jqsrt.2017.02.009 0022-4073/& 2017 Published by Elsevier Ltd.
Please cite this article as: Serdyukov VI, et al. Absorption spectrum of D2O between 10000–11000 cm-1. J Quant Spectrosc Radiat Transfer (2017), http://dx.doi.org/10.1016/j.jqsrt.2017.02.009i
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In this study, we aim to research the D216O molecule absorption spectrum in the range of 10100–10800 cm-1 using Fourier Transform techniques with light emitting diode (FT-LED). The high spectral brightness of the LED, two orders of magnitude exceeding the brightness of halogen lamps in this spectral region, provides a sufficiently high signal to noise ratio (S/N) to record weak absorption. Our results (i.e. the measured line centers and line intensities) were compared to calculated values [6] and to the results of previous measurements [3,10].
2. Experiment The absorption spectra of Н2О, HDO and D2O in the range 10100– 10800 cm –1 were recorded using a IFS-125M Fourier transform spectrometer with a spectral resolution of 0.05 cm–1 and optical path length of 24 m. A cell with base length of 60 cm and a multipass White optical scheme was used. The multipass cell uses wide-band mirrors with silver-coated protective layers of SiO2 and Al2O3 having a reflection coefficients RE98%. The measurements were performed in a temperature-stabilized room at a fixed temperature of 29771 K. The small length of the cell makes it easier to maintain a stable temperature over the entire optical path. As a radiation source, we used a EDEI-1LS3-R light-emitting diode with a high spectral brightness in the region of 0.9 μm (with a maximum in the 10370– 10670 cm-1 spectral range), which allowed us to obtain a signal-tonoise ratio of about 104 and to detect weak absorption lines with intensities on the order of 10–27 cm/molecule. To achieve a high signal-to-noise ratio, the measurements were performed over several days, and the spectrum was obtained by averaging over 8960 scans. The measurement technique with the use of light-emitting diodes is described in more detail in [12,13]. Some conditions of the present measurements are shown in Table 1. The line parameters were determined with the Wxspe software package, which is able to perform an automatic search of peaks using methods of pattern recognition theory [16]. This package allows one not only to find the peaks in the spectrum, but also to fit the contour parameters (the Voigt contour in our case) to the measured dataset by the least-squares method using the Tikhonov regularization procedure. For each parameter of the contour, its center, halfwidth, and intensity, we determined confidence intervals. For groups of overlapping lines, the parameters of all lines were fitted simultaneously. This fitting was performed taking into account the triangular instrumental function with a HWHM of 0.05 cm–1. The ambiguity in the determination of the center of isolated lines does not exceed 0.008 cm-1, and their intensity: 12%. For some weak lines for which the noise level was comparable to the signal, the centers and intensities were determined from the absorption at the line peaks. The intensities of the lines were compared with the line intensities calculated in [7] using a highly accurate ab initio dipole moment function. The analysis of the spectra in the range considered revealed more than 920 lines with intensities from 8 10–28 to 6.4 10–24 cm/molecule.
In this study, the absorption spectra of three samples were recorded: 1) mixture of H2O, D2O and HDO (at a ratio of H2O and D2O of 50:50); 2) the sample with high D2O concentration (“pure D2O”) and 3) the spectrum of water vapor with natural abundance of isotopic variants (“pure H2O”). All measurements were performed at a pressure of 27 mbar. Fig. 1 shows a transmission spectrum measured in the range under study. Note that the minimal transmission in this spectral range is T¼ 0.990; the inset shows the spectrum in a narrow range containing only very weak lines with transmission on the order of T¼ 0.9997. One can see that weak absorption lines that correspond to absorption coefficient 10-6–10-7 cm-1 are well defined by the Fourier spectrometer used in our work. Calibration of the spectrum was performed using the well isolated strong lines of the H2O molecule, which were observed in the spectrum of the gas mixture. The data of the International Union of Pure and Applied Chemistry (IUPAC) project [14] were used in our work as secondary frequency standards, since the energy levels and the centers of the Н2О lines presented there are the most precise to date. The calibration coefficient was determined by the least-squares method, which is equal to 1.000001001. The partial pressures of components of the samples are determined by using the intensities of the strongest lines of the H2O and HDO UPAC data [14,15]. The values of the partial pressures are given in Table 2. At the pressures indicated in Table 2, the intensity of the strongest line in D216O in samples 2 and 3 are the same within the measurement accuracy of 12%.
3. Results and discussion The D2O absorption spectrum in this work was investigated in the spectral range 10000–11000 cm-1. The D2O absorption spectrum in the region of 10100–10453 cm-1 is formed by transitions to the vibrational states (400), (301), (221), (122), (023), (320), (042). The D2O spectral lines in the spectral region from 10600–11000 cm-1 mainly belong to the ν1 þ3ν3 band; weak transitions of the 4ν3 band in this spectral region were observed. Line assignments in the
Table 1 Measurement conditions at 0.97 μm. Spectral resolution 0.05 cm-1 Diaphragm 1.4 mm Apodization triangle Optical path length 2400 cm Temperature 2977 1 K Scan number 8960 LED EDEI-1LS3-R Duration of measurements 12 days Pressure of mixture H2O, D2O и HDO 27 mBar Beamsplitter quartz
Fig. 1. D216O Transmission spectrum in the region 10000–11400 cm-1.
Table 2 Partial pressures of H2O, HDO and D2O in mixtures. N 1 2 3
Sample Mixture Pure D2O Pure H2O
Molecules H2OþHD D216O H2O
16
OþD216O
HDO
D216O
H2O
14 5 0
6 24 0
7 0.6 27
Please cite this article as: Serdyukov VI, et al. Absorption spectrum of D2O between 10000–11000 cm-1. J Quant Spectrosc Radiat Transfer (2017), http://dx.doi.org/10.1016/j.jqsrt.2017.02.009i
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Table 3 Statistic of the observed transitions of the D216O molecule. Band
Spectral region, cm-1
Number of assignments
Jmax.
Kamax.
Intensity
ν1 þ 3ν3 3ν1 þ ν3 4ν1 ν1 þ 2ν2 þ23 3ν1 þ 2ν2 4ν3 2ν2 þ 3ν3 4ν2 þ 2ν3 2ν1 þ 2ν2 þν3
10486–10915 10076–10482 10125–10790 10068–10442 10081–10258 10787–10970 10147–10760 10170–10445 10018–10410
175 333 88 37 21 31 7 4 224
14 16 13 14 10 12 12 11 14
7 9 7 7 5 6 5 5 8
4.6*10–24 6.4*10–24 7.9*10–25 6.9*10–25 1.8*10–25 2.9*10–26 4.7*10–25 1.1*10–25 1.2*10–24
Fig. 2. Comparison of the experimental and calculated [6] line intensities in the 10600–10800 cm-1 spectral region. Intensity ratio as a function of observed line intensity.
Fig. 3. Differences (cm-1) between experimental and calculated [6] D216O line positions in the 10100–10453 см 1 spectral region.
spectrum was carried out using the results of the large-scale variational calculations [6], based on high quality potential energy surface. The centers of lines of [6] are the best at the moment. The line list of [6] was supplemented with intensities of lines from [7], which were calculated with highly accurate vibrational-rotational wave functions and an ab initio dipole moment function of D2О. The typical error of these calculated intensities for strong lines is 5–10%. As a result of the spectrum analysis, the experimental line list was obtained, including 926 transitions to ten vibration states. All transitions are from the (000) ground vibrational state to the upper vibrational states and only one weak transition is from the (010) state to the (311) state. Statistics of the observed transitions of the D2O molecule are shown in Table 3. Table 3 gives the spectral range, a number of identified lines, the maximum value of the rotational quantum numbers J and Ka, and the maximum and minimum line intensities for bands. Table 3
max.
cm/molecule
Intensity
min.
cm/molecule
1.1*10–27 3.3*10–27 1.7*10–27 5.6*10–27 6.8*10–27 9.3*10–28 9.2*10–27 1.5*10–26 9.5*10–28
shows that the strongest bands are ν1 þ3ν3 in the region of 10600– 10800 cm-1, and 3ν1 þ ν3 in the region of 10134–10450 cm-1. A comparison of experimental intensities for lines between 10600– 10800 cm-1, where the band ν1 þ 3ν3 is situated, with the calculated intensities of [6], is shown in Fig. 2. In this study, 334 transitions belonging to the 3ν1 þ ν3 band and 89 transitions of the 4ν1 band were assigned; while in [3] 184 transitions of the 3ν1 þ ν3 band and 10 transitions of the 4ν1 band were obtained. In addition, in [3] the data on the line intensities have not been reported, only line positions are given. In this study we present a line centers, as well as their intensity. The largest deviations are observed for those D2O lines that overlap with the HDO lines; in this case, distortion of the D2O lines intensities takes place. A comparison of the intensities shows their general agreement within 15–20%. For the lines of the strongest bands ν1 þ3ν3 with an intensity higher than 5 10–25 cm/molecule, the average ratio of the experimental intensities to the calculated values is 1.1 70.07. The standard deviation of the measured lines centers from the calculated ones [6] in the region amounted to 0.036 cm-1. Fig. 3 shows a comparison of the experimental and calculated line centers for the region 10100–10453 cm-1. This figure shows that the experimental line centers are in good agreement with the calculations [6]. The maximum deviation experimental line centers to the calculated data [6] are 0.02 cm-1. The average ratio of the experimental intensities of the strongest lines in the region 10100–10453 cm-1 to the intensities calculated in [6] is 1.03 70.07. Thus, we can conclude that our measured data agree well with the data of [3] within the measurement error, and confirm the ab initio calculations of [6]. To validate the correctness of the interpretation of lines and energy levels determination, we used the software package SLON [17], which uses the Rydberg-Ritz combination principle and allows the line in automatic mode to be interpreted. This package performs line assignment by extensive use of pattern recognition methods, and uses the calculated values of the line centers and the line intensities as input data. The energy levels of the upper states were obtained by adding the center lines of a transition to the energies of the lower rotational state, and averaging over all the transitions to the same upper state. For 312 energy levels, the proposed interpretation is confirmed by the combination rule, while for other levels our assignments are confirmed by good match between observed and calculated intensities, (see Fig. 2) and regularity in the obs.- calc. differences for line positions within a bands (see Fig. 3). As a result of the spectrum analysis in the range of 10000–11000 cm-1, 530 ro-vibrational energy levels were derived, including 151 rotational sublevels of the (301) vibrational state, 106 levels of the (103) state, 67 levels of (400) state, 114 levels of (221) state, 32 levels of (122) state, 31 levels of (004) state, 20 levels of (320) state, 7 levels of (023) state and one level of the highly excited bending (042) state. All these levels correspond to rotational quantum numbers Jr 16 and Ka r9.
Please cite this article as: Serdyukov VI, et al. Absorption spectrum of D2O between 10000–11000 cm-1. J Quant Spectrosc Radiat Transfer (2017), http://dx.doi.org/10.1016/j.jqsrt.2017.02.009i
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4
Table 4 D216O rovibrational energy levels of the (301), (400), (221), (103), (122),(320),(004), (023) and (042) vibrational states between 10000 and 11000 cm-1. J
Ka
Kc
(301) Eobs.
N
s
0 1 1 1 2 2 2 2 2 3 3 3 3 3 3 3 4 4 4 4 4 4 4 4 4 5 5 5 5 5 5 5 5
0 0 1 1 0 1 1 2 2 0 1 1 2 2 3 3 0 1 1 2 2 3 3 4 4 0 1 1 2 2 3 3 4
0 1 1 0 2 2 1 1 0 3 3 2 2 1 1 0 4 4 3 3 2 2 1 1 0 5 5 4 4 3 3 2 2
10358.5619 10370.2111 10377.3146 10379.7253 10392.9494 10397.8479 10404.2259 10426.7597 10427.2730 10425.8247 10428.6198 10443.5548 10461.1619 10463.5796 10503.3932 10503.4671 10468.0129 10469.3465 10495.9234 10506.7007 10513.1127 10550.1421 10550.6261 10607.6506 10607.6507 10519.1590 10519.7118 10555.5684 10563.1266 10575.7512 10608.6490 10610.4455 10666.1861
1 3 2 2 3 3 3 2 2 4 3 3 2 3 2 2 4 4 3 4 3 3 3 2 2 3 2 3 3 3 3 2 3
1.97 0.79 0.43 5.37 0.69 1.38 0.13 0.16 3.03 4.87 0.16 3.47 0.18 2.72 0.24 6.49 4.93 2.68 0.87 2.56 2.66 0.95 3.82 2.03 5.00 0.87 3.79 4.09 0.58 2.26 0.56 2.57
5 5 5 6 6 6 6 6 6 6 6 6 6 6 6 6 7 7
4 5 5 0 1 1 2 2 3 3 4 4 5 5 6 6 0 1
1 1 0 6 6 5 5 4 4 3 3 2 2 1 1 0 7 7
10666.2579 10739.3098 10739.3123 10579.2685 10579.4652 10625.8671 10630.1705 10650.6969 10678.7626 10683.5620 10736.6726 10737.0090 10809.5268 10809.5213 10898.1295 10898.1297 10648.4201 10648.4612
3 2 2 3 3 3 5 4 5 4 3 3 3 2 2 2 3 2
1.44 3.09 0.03 2.23 2.01 5.56 5.78 4.86 5.60 2.32 4.24 1.90 4.50 1.03 0.94 1.13 1.75 2.27
7 7 7
1 2 2
6 6 5
7 7 7
3 3 4
5 4 4
10705.5322 10707.4834 10736.5837 I 10747.6000 II 10760.2331 10770.3078 10819.1184
4 4 3 3 3 3 3
10.34 9.30 0.29 5.03 0.98 2.14 0.90
7 7 7 7 7 7 7 8 8 8 8 8 8
4 5 5 6 6 7 7 0 1 1 2 2 3
3 3 2 2 1 1 0 8 8 7 7 6 6
10820.2727 10891.7115 10891.8693 10980.0880 10980.0893 11084.2851 11084.2854 10726.6586 10726.6736 10794.0366 10794.7074 10843.7679 10852.8066
3 3 3 3 3 1 1 2 2 2 5 2 3
2.62 6.66 6.89 8.09 7.12
0.28 1.70 0.86 4.22 3.36 12.73
(400) Eobs.
N
10341.0132 10352.6152 10360.1766
1 1 1
s
10380.9054
1
10408.2630 10411.7456 10426.6153 10439.6107 10443.0257 10485.0885 10485.0883 10450.5841 10452.4665 10476.9498 10485.8808 10493.1300 10532.5808
2 1 1 2 1 2 1 2 1 2 2 1 1
10590.7462 10590.7460 10501.8850 10502.7775
2 2 1 2
3.59 3.90
10542.8999
3
2.77
10592.0468 10593.0954 10650.0270 10846.3849II 10650.0256 I 10723.7010 10723.6990 10562.0853 10562.5118
2 2 2 1 1 2 1 1 1
8.42 0.08 4.31
10610.3327
1
10663.6687 10666.4372 10721.2964 10721.4965 10794.7347 10794.7238 10883.8150 10883.8206 10631.3268 10631.4836 I 10828.6712 II
2 2 1 2 1 2 1 1 1 2 1
10753.2860 10804.6101I 11000.5329II
1 2 1
10877.7070 10877.6229 10966.6711 10966.7051
1 1 1 1
10774.9375
1
11.40
1.36 5.59 7.75 12.09 2.94
1.03
1.99
0.63 7.39 0.37 10.59
4.03
5.5
(221) Eobs.
N
s
(103) Eobs.
N
s
10180.1181 10191.9086 10201.4125 10204.0974 10215.0008 10222.6544 10230.4688 10258.7489 10259.2233 10248.4628 10251.4518 10269.5445 10293.5689 10295.8196 10347.8325 10347.8832 10291.3988 10293.6301 10320.8031 10339.7720 10345.6748 10395.3221 10395.7116 10468.6875 10468.7389 10343.2671 10344.4605 10383.4639 10397.1684 10408.3943 10454.7953 10456.2770 10528.1335
1 2 2 2 2 3 3 2 2 3 2 3 3 3 2 2 2 3 2 4 3 3 3 2 2 3 2 3 3 3 3 3 3
3.05 2.04 0.50 12.53 1.07 3.82 3.89 6.88 7.72 4.37 1.41 4.72 5.79 1.04 0.06 2.28 0.58 0.75 1.00 9.63 6.08 7.21 6.39 6.65 4.58 4.17 2.14 2.48 4.24 5.65 3.32 2.53
10691.3838
2
0.99
10700.5574 10714.2121 10719.0481 10726.4286 10746.4973 10747.0597 10747.2349 10750.1432 10764.8029 10781.6355 10784.2743 10821.3309 10821.4426 10789.5938 10791.1196 10815.0704 10828.0593 10835.0276 10869.1718 10869.7558 10922.9521 10922.9464 10840.9744 10841.6010 10876.3214 10885.2636 10899.1630 10928.9738 10931.0418 10983.0619
2 2 3 2 2 2 2 2 2 1 2 2 1 2 1 2 1 2 3 2 1 1 2 2 2 3 4 1 3 2
0.60 14.16 1.84 1.48 0.52 3.92 1.57 1.53 2.18
10528.2824 10620.6017 10620.6053 10403.9644 10404.5140 10456.5323 10465.4717 10493.2646 10526.1349 10530.1845 10599.5767 10600.0688 10691.9221 10691.9119 10802.1550 10802.1551 10473.5631 10473.8031
3 2 1 2 3 1 3 2 3 2 3 2 2 2 2 2 2 2
2.36 4.02 1.33 7.93 2.71 3.62 6.42 10.86 23.30 23.10 0.08 4.56
10983.1489 11051.1402 11051.1428 10901.3783 10901.6124 10947.5022 10952.9353 10975.9938 11000.5283 11005.9527 11055.3494 11055.7552 11123.6460 11123.6374 11205.4303 11205.4302 10970.9655 10970.9412
3 2 2 3 2 1 2 3 4 2 4 2 2 1 1 1 2 1
10538.9852 10544.2591 10582.1682
1 3 3
2.10 2.37
11027.8679 11030.6568 11064.2597
3 2 1
2.76 1.84
10609.0607 10617.9188 10682.6370
2 3 3
1.99 3.74 1.80
11083.4536 11094.7560 11139.7618
2 2 1
2.59 7.82
10684.3855 10775.3837 10775.4264 10885.0497 10885.1649 11011.3393 11011.3395 10551.9685 10552.2393 10630.1889 10633.0365
3 2 3 1 1 1 1 2 1 2 2
2.25 0.05 3.98
11141.1124
3
3.27
11208.1726 11291.1322 11291.1318
2 1 1
6.67
2 2 1 3
15.93 2.99
1.68 4.12
11049.9985 11049.6205 11117.2190 11118.1198
2.63
10704.6844
3
6.74
11177.3113
2
13.94
0.43 4.16 0.34 8.41
1.2
1.72 16.15 0.76 0.43 8.46 3.18 20.20
6.31 7.28 1.88 2.49 3.17 5.06 6.05 7.80 0.34 2.77 6.22 3.33 2.22 6.58 5.12 3.01 2.58 5.27 2.98
2.38
Please cite this article as: Serdyukov VI, et al. Absorption spectrum of D2O between 10000–11000 cm-1. J Quant Spectrosc Radiat Transfer (2017), http://dx.doi.org/10.1016/j.jqsrt.2017.02.009i
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5
Table 4 (continued ) J
Ka
Kc
(301) Eobs.
N
s
(400) Eobs.
N
8 8 8 8
3 4 4 5
5 5 4 4
10869.8842 10913.4471 10916.6484 10985.8746
4 3 3 3
6.90 3.50 2.83 0.97
10853.6366 10899.8450
1 1
10972.6252I 11170.8019II
1 1
8 8 8 8 8 8 8 9 9 9 9 9 9
5 6 6 7 7 8 8 0 1 1 2 2 3
3 3 2 2 1 1 0 9 9 8 8 7 7
10986.1740 11073.9605 11073.9585 11178.2612 11178.2613 11300.0240 11300.0242 10814.0108 10814.0467 10891.3976 10891.4929 10951.1104 10956.1154
2 2 2 2 2 2 2 2 2 3 3 3 4
8.97 4.43 6.75 1.48 1.82 1.92 2.09 7.87 3.88 1.51 3.48 6.13 4.90
9 9 9 9
3 4 4 5
6 6 5 5
10983.7555 11019.4671 11026.5653 11092.0615
3 2 2 2
3.82 0.95 0.62 2.76
9 9 9 9 9 10 10 10 10 10 10 10 10
5 6 6 7 7 0 1 1 2 2 3 3 4
4 4 3 3 2 10 10 9 9 8 8 7 7
11092.8887 11179.8778 11179.8612 11283.6254 11283.6250 10910.4559 10910.4698 10997.8541 10997.6192 11066.2032 11068.7796 11107.8982 11136.8653
3 2 2 1 1 3 2 2 2 2 2 2 3
3.61 13.92 7.00
10 10 10 10 10 10 10 10 11 11 11 11 11 11 11 11 11 11 11
4 5 5 6 6 7 7 8 0 1 1 2 2 3 3 4 4 5 5
6 6 5 5 4 4 3 3 11 11 10 10 9 9 8 8 7 6 7
11150.3560 11210.2784 11212.3149 11298.1404 11297.8190
2 3 2 2 2
6.69 4.08 9.03 13.88 0.70
11 11 11 11 11 12 12 12 12 12 12 12 12 12 12 12 13
6 6 8 9 9 0 1 2 2 3 3 4 4 5 5 6 0
6 5 4 3 2 12 12 11 10 10 9 9 8 8 7 6 13
3.82 2.28 11.43 3.54 2.54 0.26 0.55 9.41
11016.0431 11016.0575 11112.8757 11113.1123 11191.9067 11191.4273 11256.5491 11265.2727
2 2 2 1 1 2 2 2
0.67 9.11 6.20
11344.9423 11340.3577
3 1
2.82
11428.6921 11428.0074
2 1
14.63
11754.2461 11754.2460 11130.7226 11130.7161 11238.0996 11326.9691 11327.1365
1 1 2 2 2 1 1
11403.8892 11437.6745 11481.8792 11491.3306
1 1 1 2
11254.5479
1
0.54 0.13 1.45
11061.4691 11165.2287
1 1
10936.8055 I 11142.1170 II
2 1
1.33
11007.0118 11011.6073 11079.4788I 11280.3823II
3 1 1 1
6.55
11272.9023
2
10893.1230 10893.0677
1 1
11248.4592
II
1 1
11383.3374
1
II
10998.5352 10998.6075
11241.9018
(221) Eobs.
N
s
(103) Eobs.
N
s
10719.4718 10778.1048 10781.6413 10871.0986
2 1 3 2
0.95 6.97 4.92
11197.0446 11236.1568 11239.9567 11305.1193
2 2 3 3
0.73 7.21 4.62 6.82
10871.7432 10980.2630 10980.2444 11105.4192 11105.4189
2 2 1 1 1
2.50 6.60
11388.9144
1
11487.0942 11487.0940
1 1
10639.6552 10639.7419 10729.9577 10731.4305 10798.6874 10809.9513
1 2 2 1 3 2
11134.4151 11138.3840 11216.1921 11215.2083
2 1 1 2
11281.5582
1
10834.0296 10889.7952 10892.3416 10979.1803
1 2 2 2
4.37 22.12 6.15
11311.9706 11344.2274 11352.2929
2 2 3
10978.7346 11087.5471
3 2
6.37 24.86
10736.2878 10736.3209 10838.3790 10838.7695
2 2 2 1
18.19 4.12 6.05
11233.5556 11232.7211
1 1
10926.2694
2
7.45
11395.8726
1
11008.3954
1
11463.4999
2
3.10
11016.8363
1
11478.5664 11534.9474
3 2
12.79 1.71
11099.4021 11207.0468 11206.9663 11330.3005 11330.3049 11525.6437 10841.9118 10841.9359 10955.6069
1 3 1 2 2 1 1 1 1
11339.3712 11339.2158
1 1
11518.7254 11574.3849
1 3
11673.0014
1
11454.5727 11454.5751
1 1
11718.8324
1
11770.3160
2
7.07
11578.9010
2
4.10
8.05 0.15 2.87 2.54
2.38
19.20
0.45 8.52 3.22
1.70
1
11125.9835I 11327.6299II
11509.6944I 11534.1823II
7.33 1.51 5.33
s
1 1
1
5.27 22.12 15.45
4.58
0.62 11154.9735 11232.8630
1 1
11657.5231
1
10957.2200
1
11186.2286
1
1
19.24 11482.6561
1
Please cite this article as: Serdyukov VI, et al. Absorption spectrum of D2O between 10000–11000 cm-1. J Quant Spectrosc Radiat Transfer (2017), http://dx.doi.org/10.1016/j.jqsrt.2017.02.009i
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6
Table 4 (continued ) J
Ka
Kc
(301) Eobs.
N
s
13 13 13 13 13 13 13 14 14 14 14 14 14 14 14 15 15 15 15 16 16
1 1 2 2 3 3 5 0 1 1 2 3 3 4 5 0 1 1 2 0 0
13 12 12 11 11 10 8 14 14 13 13 12 11 11 10 15 15 14 13 16 16
11254.4569 11371.2146 11371.6528 11470.1495 11469.3629 11558.9212 11651.4012 11387.2090 11387.2091
2 2 1 1 2 1 1 1 1
0.34 0.91
11514.2166 11621.5107
1 2
J
Ka
1 1 2 2 2 3 3 3 3 3 3 4 4 4 4 4 4 4 5 5 5 5 5 5 5 6 6 6 6 6 6 6 6 6 7 7 7 8 8 8 8 8 9 9 9 9 9 9 9 9
0 1 0 2 2 1 1 2 2 3 3 0 1 2 3 3 4 4 1 2 2 3 3 4 5 1 2 2 3 3 4 5 6 6 1 3 5 0 1 2 3 5 1 2 3 4 5 5 7 7
Kc
1 1 2 1 0 3 2 2 1 1 0 4 3 2 2 1 1 0 5 4 3 3 2 2 1 5 5 4 4 3 2 1 1 0 6 5 3 8 7 7 5 3 9 8 7 6 5 4 3 2
11529.0124 11529.0124 11660.0210 11780.7316 11679.8300 11679.8292 (122) Eobs.
2 2 1 1 1 1 N
(400) Eobs.
s
10448.3088 10450.2294 10498.4722
3 1 1
5.97
10500.9602 10546.7445 10547.1498
3 1 1
6.33
10550.9345
4
5.47
10608.6894
1
(023) Eobs.
N
10506.7681
1
10570.4612
10659.9896
1 1
10700.7855 10785.4021 10787.1862
1 3 2
11022.5966 10788.6867 10885.6195
1 1 1
11217.0900
1
s
1 1
s
(320) Eobs.
N
s
(103) Eobs.
N
s
11578.9036 11692.2796
2 1
6.08
11790.6854
1
11984.6323
1
11835.2042 11835.1889
1 1
12037.8888 12051.2344 12143.9948 11854.7500
1 1 1 1
11987.0407
1
(004) Eobs.
N
10879.2852 10895.9338
1 1
10927.4457 10931.7013 10946.5567 10962.2427
1 1 1 1
11000.2422 11000.3383 10971.5943 10997.1184
1 1 1 1
11049.0981 11099.8397 11099.8689 11023.7422 11066.5602 11081.1420 11108.7673
1 1 1 1 1 1 1
11160.3795 11225.4208
1 1
11134.6484 11158.6669 11180.7966 11186.8828 11233.6756 11298.2344 11376.5258 11376.5428
1 1 1 1 1 1 1 2
11264.2355
1
11379.9223
1
11463.4624
1
s
1 10216.5763
1
10255.6833
2
10307.9924
1
10304.7274 10356.5874
1 1
9.04
1
4.95
10743.0309
1
10839.9147
1
10854.3178 10947.6639
1 3
17.54
12.57 0.08
11286.7602 11287.2561 11347.7690 11347.7691
N
0.52 1.24
21.34
10693.4621 10763.5587
(221) Eobs.
11359.9273 11487.4827
3.36
2 1
1 2
s
4.52
10412.7144 10413.1087
10611.2256 10619.6709
N
1 1
16.02
1 1
Please cite this article as: Serdyukov VI, et al. Absorption spectrum of D2O between 10000–11000 cm-1. J Quant Spectrosc Radiat Transfer (2017), http://dx.doi.org/10.1016/j.jqsrt.2017.02.009i
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7
Table 4 (continued ) J
Ka
Kc
10 10 10 10 10 10 11 11 11 12 13 14
1 2 2 5 7 7 1 2 2 1 2 1
9 9 8 6 4 3 10 10 9 11 12 13
J
Ka
Kc
11
5
7
(122) Eobs.
N
s
10990.0486 10994.2951 11071.3272
1 1 2
9.65
11465.5270 11465.5269 11107.1840 11104.2941
1 1 1 2
11232.9580 11365.3823 11508.1256
2 1 2
8.43
N 4
s 7.72
(042) Eobs. 11189.5411
(023) Eobs.
N
s
(320) Eobs.
N
11069.8773
1
s
(004) Eobs.
N
11748.0733
1
s
13.18 11362.7703 11398.9897
1 1
2.91
Notes: Eobs. is observed upper energy level, J, Ka, Kc - rotational quantum numbers,. N is the number of lines used for the upper energy level determination, s (in10-3 cm-1) denotes the rms-statistical error of the deviation of the levels derived through several transitions. Roman numerals I and II denote the levels having the same set of approximate quantum numbers but should be referred to different states on the base of calculation of Ref [11].
The energy levels obtained here were compared with the experimental energy levels obtained in [10] using a Fourier Transform Spectrometer with a long absorption cell. The standard deviation of our data from data of [10] for the ν1 þ3ν3 band is 0.005 cm-1, for the 2ν1 þ2ν2 þ ν3 band is 0.0015 cm-1, and for the 4ν1 band is 0.012 cm-1. This shows good agreement with our experimental data, and the data obtained in [10]. Thesis [10] is not contain the D2O linelist and only energy levels. In comparison with [10] 101 new energy levels belonging to nine vibrational states were derived in our work, including 31 energy levels of the (004) state and one energy level of the (042) vibrational state, which were not investigated in [10]. The frequencies determined here coincide with those obtained in [3] within the accuracy of measurement, but with the exception of some number of lines caused by transitions to the rotational levels [10 1 9],[11 2 10] and [13 0 13] of the vibrational state (301). For these lines, the differences between our values and those of [3] are 0.122 cm-1, 0.347 cm-1, and 0.161 cm-1, respectively. This large difference is caused by the fact that in [3], the HDO lines were falsely attributed to D2O. These three rotational levels are different to the recommended UIPAC data [5] by more than 0.1 cm-1, which is beyond the scope of experimental error. For these lines, Δ ¼Eexp-EIUPAC is equal 0.122 cm-1, 0.347 cm-1, and 0.161 cm-1, respectively. This is because the wrong energy levels of [3] were transferred to the recommended database of the D216O levels. At the same time, our measured energy levels coincide with the calculated ab initio data [6] within the measurement accuracy: the differences do not exceed 0.023 cm-1. The entire set of energy levels is given in Table 4. The accuracy of the observed energy levels is 0.004 cm-1 on average for levels confirmed by the combination differences. The calculations [6] give in some cases the same quantum numbers for levels with different energy. The vibrational problem for the D2O molecules using the method of effective Hamiltonians was solved in [11], where the mixing coefficients of the wave functions were determined. For the vibrational level 10538.494 cm-1 the mixing coefficients are equal to 0.503 and 0.420 for the states (202) and (400), respectively [11]. In the Table 4 Roman numerals I and II denote the levels having the same set of approximate quantum numbers but should be referred to different states on the base of calculation of [11]. Energy levels marked by Roman numerals II should be assigned to (202) vibrational state with the same rotational quantum numbers (for example, the level (400) [542] at 10846.3849 cm-1). Also, (301) [725] level at 10747.6000 cm-1 can be attributed to (400) [735]
rovibrational state because of strong Coriolis resonance. A line list that contains more than 920 D2O transitions is attached to this paper in the Supplementary Materials. The complete dataset containing all the detected transitions is available at http://wadis.saga.iao.ru.
4. Conclusions Using the LED-based Fourier Transform spectrometer allowed us to measure the line positions and strengths of weak absorption lines of D2O molecules near 0.97 μm. The analysis of the spectrum resulted in spectroscopic line parameters that are in good agreement with the calculated data [6] and experimental data [3,10]. We have determined the rotational energy levels of nine vibrational states: (301), (103), (400), (221), (122), (320), (023), (004) and (042). New 101 energy levels were derived from the experiment. The weak (004) and (042) vibrational states were studied for the first time. New measured line centers, intensities, as well as a set of experimentally derived vibration-rotational energy levels can be used further to clarify the absorption capability of D2O and its internal dynamics.
Acknowledgements This work is partly supported by RFBR (Grants No. 16-43700492 and No.17-03-00437 А). The authors express their gratitude to O.V. Naumenko for useful discussions of the vibration-rotation assignment of the D2O lines and to A.S.Sergeeva and T.V.Kruglova for help in spectra analysis.
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.2017.02.009.
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Please cite this article as: Serdyukov VI, et al. Absorption spectrum of D2O between 10000–11000 cm-1. J Quant Spectrosc Radiat Transfer (2017), http://dx.doi.org/10.1016/j.jqsrt.2017.02.009i
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Please cite this article as: Serdyukov VI, et al. Absorption spectrum of D2O between 10000–11000 cm-1. J Quant Spectrosc Radiat Transfer (2017), http://dx.doi.org/10.1016/j.jqsrt.2017.02.009i