Infrared spectroscopy of 17O- and 18O-enriched carbon dioxide: Line positions and intensities in the 4681–5337 cm−1 region

Journal of Quantitative Spectroscopy & Radiative Transfer ] (]]]]) ]]]–]]]

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Journal of Quantitative Spectroscopy & Radiative Transfer

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

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Infrared spectroscopy of 17O- and 18O-enriched carbon dioxide: Line positions and intensities in the 4681–5337 cm
1 region

17 Q1

Yu.G. Borkov a, D. Jacquemart b,c, O.M. Lyulin a, S.A. Tashkun a,d, V.I. Perevalov a,n

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a Laboratory of Theoretical Spectroscopy, V. E. Zuev Institute of Atmospheric Optics, Siberian Branch, Russian Academy of Science, 1, Akademician Zuev sq., 634021 Tomsk, Russia b Sorbonne Universités, UPMC Univ Paris 06, UMR 8233, MONARIS, F-75005 Paris, France c CNRS, UMR 8233, MONARIS, F-75005 Paris, France d Tomsk State University, Laboratory of Quantum Mechanics of Molecules and Radiative Processes, Lenin av. 36, 634050 Tomsk, Russia

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a r t i c l e i n f o

abstract

Article history: Received 13 October 2014 Received in revised form 20 February 2015 Accepted 21 February 2015

The line positions and intensities of carbon dioxide isotopologues have been retrieved in the 4681–5337 cm
1 spectral range from Fourier transform spectra of carbon dioxide recorded in LADIR (Paris, France) with the Bruker IFS 125-HR [Jacquemart D, et al., J Quant Spectrosc Radiat Transf 2012;113:961–975]. In total 6386 line positions and intensities of 89 bands of 12 isotopologues 16O12C16O, 16O13C16O, 16O12C18O, 16O12C17O, 16O13C18O, 16 13 17 O C O, 18O12C18O, 17O12C18O, 17O12C17O, 18O13C18O, 17O13C18O, and 17O13C17O have been retrieved. 23 bands were newly assigned. All studied bands belong to the ΔP¼ 7 series of transitions, where P ¼ 2V 1 þ V 2 þ 3V 3 is the polyad number (Vi are vibrational quantum numbers). The accuracy of the line position measurement is about 0.3  10
3 cm
1 for the unblended and not very weak lines. The accuracy of the line intensities varies from 4% to 15% depending on the isotopologue, on the intensity of the line and on the extent of the line overlapping. The observed intensities were used to fit the effective dipole moment parameters for the ΔP ¼ 7 series of transitions in 16O12C18O, 16O12C17O, 12C17O2, 17O12C18O, 16 13 17 O C O, 13C17O2 and 17O13C18O isotopologues of carbon dioxide. & 2015 Published by Elsevier Ltd.

31 33 35 37 39

Keywords: Carbon dioxide Isotopologues Infrared Line positions Line intensities Global modelling HITRAN GEISA CDSD

41 63

43 45 47 49 51 53

1. Introduction This paper continues the series of our publications devoted to the analysis of the spectra of carbon dioxide enriched in 17O and 18O, which were recorded in LADIR (Paris, France) in the 1700–9000 cm
1 wavenumber range [1–3]. The aim of this research is to provide spectroscopic reference data for the remote sensing of the planetary atmospheres of Mars, Venus and Earth. The information about spectral line parameters of 17OCO isotopologues

55 57 59

n

Corresponding author. E-mail address: [email protected] (V.I. Perevalov).

contained in the existing databases HITRAN2012 [4], CDSD [5–7], OCO [8] and AMES [9] either is not complete or needs to be validated because the majority of the line parameters are taken to these databases from the calculations. The first paper of this series [1] is devoted to establishing of the isotopic composition of the sample used in LADIR. The second paper [2] deals with the assignment of the spectra recorded in LADIR and in USTC (Hefei, China). In the third paper [3] the 3200–4700 cm
1 region corresponding to the ΔP ¼5 and ΔP ¼6 series of transitions was carefully studied. Here P is a polyad number. P ¼2V1 þ V2 þ3V3, where Vi (i¼1, 2, 3) are harmonic oscillator quantum numbers. In that work, a number of new bands were assigned and the line positions measured

http://dx.doi.org/10.1016/j.jqsrt.2015.02.019 0022-4073/& 2015 Published by Elsevier Ltd.

61 Please cite this article as: Borkov YuG, et al. Infrared spectroscopy of 17O- and 18O-enriched carbon dioxide: Line positions and intensities in the 4681–5337 cm
1 region. J Quant Spectrosc Radiat Transfer (2015), http://dx.doi.org/10.1016/j. jqsrt.2015.02.019i

65 67 69 71 73 75 77 79 81

Yu.G. Borkov et al. / Journal of Quantitative Spectroscopy & Radiative Transfer ] (]]]]) ]]]–]]]

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for the 16O12C17O and 17O12C17O isotopologues were used, together with those collected from the literature, to fit the effective Hamiltonian parameters. The retrieved line intensities were used to fit the effective dipole moment parameters for the ΔP ¼5 and ΔP ¼6 series of transitions in 16 12 17 O C O, 12C17O2 and 16O12C18O. In this paper we study the 4681–5337 cm
1 region, corresponding to ΔP¼ 7 series of transitions. A number of new bands of 16O12C17O, 12C17O2, 16O13C17O, 17O12C18O, 17 13 18 O C O and 13C17O2 isotopologues were assigned. In the result of the multispectrum fitting the line positions and line intensities were determined. The line intensities obtained in this work were used to fit the effective dipole moment parameters for the ΔP¼7 series of transitions in 16 12 18 O C O, 16O12C17O, 12C17O2, 17O12C18O, 16O13C17O, 13 17 C O2 and 17O13C18O. The line positions determined in this work have already been used for the refinement of the effective Hamiltonian parameters of nine isotopologues: 16 12 18 O C O [10]; 16O13C18O, 12C18O2 and 13C18O2 [11]; 12 17 C O2 and 16O12C17O [3]; 17O12C18O, 16O13C17O and 17 13 18 O C O [12].

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2. Experiment

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Line parameters in the 4681–5337 cm
1 region have been retrieved from the spectra recorded in LADIR (Paris, France) [1] using a carbon dioxide sample enriched in 17O and 18O. The detailed description of the experiment is presented in our paper [1]. Thirteen spectra were recorded at room temperature using a rapid scan interferometer Bruker IFS 125 h with unapodized resolution of 0.0056 cm
1 and a metal multipass White-type cell (1-m base length). The whole optical path was under vacuum and the multipass cell was aligned to provide absorption path lengths between 4.15 and 20.15 m. The temperature inside the cell was stable to 70.3 K during the recording. The experimental conditions of the spectra recordings are gathered in Table 1 of the above cited paper [1]. The obtained concentrations of the carbon dioxide isotopologues in the sample are presented in Table 2 of that paper. In Fig. 1 we present the overview spectrum of this sample in the 4681–5337 cm
1 region that has been studied in this work.

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3. Retrieval of the spectral line parameters

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The spectral line parameters were retrieved using multispectrum fitting procedure in which a nonlinear least-squares method is applied simultaneously to a set of spectra recorded under various experimental conditions. Within this procedure the computer code determines line parameters by adjustment of the synthetic spectra to the observed ones. The adjustable parameters include position, intensity, self-broadening and self pressure induced shift coefficients of each line and the parameters of a base line, which is modelled by a second order polynomial. The spectral line shape was modelled with the Voigt profile in which the calculated value for the Doppler line width was used. The apparatus function was modelled by an apodized sinc function using an average value of the effective iris radius equal to 0.625 mm (see Ref. [1]). The

1 3 5 7 9 11 13 15 17 19

27 29 31 33 35 37 39 41

49 51 53 55 57 59 61

initial values for the broadening coefficients were taken from Ref. [13]. In the cases of the overlapped lines the broadening coefficients were fixed to the values from [13] and average value for the self pressure induced shift coefficients equal to –0.01 cm
1/atm was used. In Fig. 2 a fragment of the observed spectra and the residuals between the observed and simulated spectra are given. The above described procedure with the calibration performed in our previous paper [1] allowed us to get the line positions with the absolute accuracy on the level of 0.0003 cm
1 for the unblended and not very weak lines. The uncertainties of the line intensities vary from 4% to 15% and depend mostly on the uncertainties of the isotopologue abundances in the sample [1]. The line assignment has been done using the predictions performed with the effective Hamiltonians published in the following papers: 12C16O2 [14]; 13C16O2 [15]; 16 12 17 O C O and 12C17O2 [3]; 16O12C18O [10]; 16O13C18O, 12 18 C O2 and 13C18O2 [11]; 17O12C18O, 16O13C17O and 17 13 18 O C O [12]. In this paper we present 23 new assigned bands in the 4681–5337 cm
1 region in addition to those published in our recent paper [2]. The summary of the bands studied is presented in Table 1. The recovered line positions and intensities are given as the Supplementary Material.

63 65 67 69 71 73 75 77 79 81 83 85 87 89

4. Comparison to previous measurements 91 In Fig. 3 we give a comparison of our measured line positions to those from Refs. [16–18] for the principal isotopologue 12C16O2. As one can see from this figure there is very good agreement for the majority of the lines between our measured line positions and those from Ref. [16]. It is not surprising because the very precise measurements from that paper were used for calibration of our spectra. The relatively large residuals for some very weak lines are connected with the line overlapping in our spectra. In Fig. 4 we give as another example a comparison of our measured line positions to those from Refs. [19–21] for 16O12C18O. This figure shows that there is very good agreement between our measured line positions and those precisely measured in Ref. [21]. We have also compared our measured line positions to those from Ref. [21] for 17 12 18 O C O. The comparison is presented in Fig. 5. Again there is a good agreement between our measured line positions and those from Ref. [21] for cold bands 2001i– 00001 (i¼ 1, 2, 3) but there are relatively large residuals for the hot band 21112–01101. The lines of this hot band are very weak and are blended in both our spectra and in that from Ref. [21]. The line positions in the considering region for 16O12C17O were measured before only in Venus and Mars spectra [22]. The respective measured line positions were used by us to fit the effective Hamiltonian parameters for this isotopologue in our early paper [23]. So it is very interesting to compare the new measured line positions to those obtained from Venus and Mars spectra [22]. The respective comparison is presented in Fig. 6. As one can see from this figure the line positions obtained from Venus and Mars spectra [22] are shifted from our values on the average on –0.002 cm
1.

Please cite this article as: Borkov YuG, et al. Infrared spectroscopy of 17O- and 18O-enriched carbon dioxide: Line positions and intensities in the 4681–5337 cm
1 region. J Quant Spectrosc Radiat Transfer (2015), http://dx.doi.org/10.1016/j. jqsrt.2015.02.019i

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Yu.G. Borkov et al. / Journal of Quantitative Spectroscopy & Radiative Transfer ] (]]]]) ]]]–]]]

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Transmission in arbitrary units

1

25 27

4600

4700

4800

4900

5000

W avenumber, cm

5100

5200

87

5300

-1

Fig. 1. Overview spectrum in the 4681–5337 cm
1 region of the carbon dioxide sample described in Ref. [1]: P¼ 31.42 Torr, L ¼2015 cm, T ¼ 297.7 K.

91

29 5. Band-by-band analysis

6. Fitting of the line intensities

In the case of isolated vibrational state the vibration– rotation energies of linear molecules can be expressed as

All observed bands in the 4681–5337 cm
1 region belong to the ΔP ¼7 series of transitions. In this paper we present the results of the global modelling of the line intensities in this region for seven isotopologues: 16 12 18 O C O, 16O12C17O, 12C17O2, 17O12C18O, 16O13C17O, 13 17 C O2 and 17O13C18O. The modelling is performed using the method of effective operators. The line intensity is proportional to the transition dipole moment squared, which within the used approach is presented by the following equation [27–29]:

93

31 33

2

35 37 39 41 43 45 47 49

2

3

3

F v ðJÞ ¼ Gv þ Bv JðJ þ 1Þ
Dv J ðJ þ1Þ þH v J ðJ þ 1Þ ;

ð1Þ

where Gv is the vibrational term value, Bv is the rotational constant, Dv and Hv are centrifugal distortion constants, and J is the angular momentum quantum number. The spectroscopic constants were fitted to the measured line positions. The e and f sub states were considered independently. The lower state constants were constrained




W P0 N0 J 0 ε0 ’PNJε ¼ ð2J þ 1Þ



X

X

J

2V 1 þ V 2 þ3V 3 ¼ P 2ΔV 1 þΔV 2 þ 3ΔV 3 ¼ ΔP

V 1 V 2 ℓ2 V 3 J 0

C PNε

Δℓ2 j 1 V 2 þ ΔV 2 ℓ2 þ Δℓ2 V 3 þ ΔV 3 : C VP 01Nþ0 εΔV MjΔV 0

ℓ2 Δℓ2 ¼ 0; 71; 7 2; :::
2 ! rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
  X
Δℓ ΔV  f ΔV2 ðV; ℓ2 Þ 1 þ δℓ2 ;0 þ δℓ02 ;0
2δℓ2 ;0 δℓ02 ;0 1 þ κ ΔV V þ b m Φ ðJ; ℓ Þ
: ΔJ; Δℓ 2 i m i 2


99 101 103

109 ð2Þ

i

111 113 115

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61

97

107

53

59

95

105

51

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89

to the values from Refs. [24–26]. In the case of upper states observed through different bands, a global fit was performed in order to provide a unique set of parameters for each upper state. The retrieved spectroscopic constants are listed in Table 2 for the newly observed bands and those for known bands are given in the Supplementary Material II.

V V ℓ V

0

V þ ΔV V þ ΔV ℓ þ Δℓ V þ ΔV

1 2 2 3 2 2 2 3 3 In this equation J C PNε and J C P01N'ε' 1 2 are the expansion coefficients of the eigenfunctions for lower and upper states, respectively, in the bases of harmonic oscillators and rigid symmetric top eigenfunctions, δi;j is the Kronecker symbol, m ¼
J for P-branch andm ¼ J þ1 for Δℓ R-branch. The functions f ΔV2 ðV; ℓ2 Þ are known functions of

Please cite this article as: Borkov YuG, et al. Infrared spectroscopy of 17O- and 18O-enriched carbon dioxide: Line positions and intensities in the 4681–5337 cm
1 region. J Quant Spectrosc Radiat Transfer (2015), http://dx.doi.org/10.1016/j. jqsrt.2015.02.019i

117 119 121 123

8 R 13 20012-00001 e

8 R 25 21112-01101 e 9 P 8 22212-02201

3 P 34 20012-00001 e 9 P 30 20012-00001 e

3 P 25 21112-01101 f

3 R 10 30013-10002 e

8 R 24 21112-01101 f

9 P 21 21112-01101 f 2 P 14 20012 00001 e 9 R 16 30013 10002 e

3 P 25 21112-01101 e

4 P 65 20012-00001 e 1 R 30 20013-00001 e

8 R 12 20012-00001 e 8 R 24 21112-01101 e 9 P 21 21112-01101 e

6 R 42 20012-00001 e

9 P 9 22212-02201

3 R 9 30013-10002 e 8 R 23 21112-01101 f

9 R 15 30013-10002 e

9 P 31 20012-00001 e

5

8 R 23 21112-01101 e

3

9 P 22 21112-01101 f 8 R 11 20012-00001 e 6 R 41 20012-00001 e

3 P 26 21112-01101 e

Assignment

1

3 P 35 20012-00001 e

Yu.G. Borkov et al. / Journal of Quantitative Spectroscopy & Radiative Transfer ] (]]]]) ]]]–]]]

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0.30

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9 11 13 15 17 19

Transmission in arbitrary units

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3 0.20

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0.10

0.05

25 27

35 37 39

77

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11 12

49 51 53 55 57 59 61

85

89

-0.002 4875.09

4875.26

4875.43

4875.60

4875.77

4875.94

4876.11

4876.28

91

Wavenumber, cm-1
1 Q3 Fig. 2. Observed and simulated spectra of the carbon dioxide sample from Ref. [1] in the 4874.1–4876.4 cm spectral interval. In the upper part of this

figure the line assignment is presented. The first character in the line label denotes isotopologue: 1–626, 2–636, 3–628, 4–627, 6–637, 8–728, 9–727. On the middle panel the observed spectra at room temperature are given: 1 – P¼ 31.42 Torr, L ¼ 2015 cm; 2 – P ¼15.00 Torr, L ¼ 2015 cm; 3 – P¼ 7.551 Torr, L ¼ 2015 cm; 4 – P¼ 7.551 Torr, L ¼ 815 cm; 5 – P ¼7.551 Torr, L ¼415 cm; 6 – P¼2.971 Torr, L ¼ 415 cm; 7 – P¼ 1.4315 Torr, L ¼415 cm; 8 – P ¼0.6577 Torr, L ¼ 415 cm; 9 – P¼ 0.3007 Torr, L ¼ 415 cm; 10 – P ¼0.1128 Torr, L ¼ 415 cm; 11 – P¼ 0.0695 Torr, L ¼415 cm; 12 – P ¼0.0366 Torr, L ¼ 415 cm. On the bottom the residuals between the observed and simulated spectra are given in the same units as transmittance. The largest residuals correspond to the saturated lines. In the multispectrum fitting the central part of these lines was not considered. (For interpretation of the references to colour in this figure, the reader is referred to the web version of this article.)

93 95 97 99 101

Table 1 Summary of the studied bands.

103 Isotopologue Number of observed bands

Number of observed lines

Number of newly observed bands

Number of newly observed Newly measured line lines intensities

45 47

83

87

41 43

81

0.000

29

33

75

7

10

4874.92

31

73

9

0.002

Residuals

23

71

6

0.00

21

69

2

0.25

16

O12C16O O13C16O 16 12 18 O C O 16 12 17 O C O 16 13 18 O C O 16 13 17 O C O 18 12 18 O C O 17 12 18 O C O 17 12 17 O C O 18 13 18 O C O 17 13 18 O C O 17 13 17 O C O Total 16

15 3 9 16 3 4 5 12 16 1 2 3 89

768 99 840 1523 103 238 230 959 1351 7 99 169 6386

– – – 7 – 1 – 4 9 – 1 1 23

the vibrational quantum numbers. They are listed in Table 1 of Ref. [28] for small values of the quantum number differences ΔV. The functions ΦΔJΔℓ2 ðJ; ℓ2 Þ for Δℓ2 ¼ 0; 71 are equal to

– – – 299 – 8 – 126 371 – 31 51 886

Number of bands

Number of lines

– – 3 13 – 2 – 5 16 – 2 2 43

– – 65 1125 – 71 – 260 1352 – 99 138 3110


the Clebsch–Gordan coefficientsð1Δℓ2 Jℓ2
ðJ þ ΔJÞ ðℓ2 þ Δℓ2 ÞÞ. Δℓ2 j The principal parameters M jΔV and Herman-Wallis type ΔV parameters bm and κΔV of the matrix elements of the effective i

Please cite this article as: Borkov YuG, et al. Infrared spectroscopy of 17O- and 18O-enriched carbon dioxide: Line positions and intensities in the 4681–5337 cm
1 region. J Quant Spectrosc Radiat Transfer (2015), http://dx.doi.org/10.1016/j. jqsrt.2015.02.019i

105 107 109 111 113 115 117 119 121 123

Yu.G. Borkov et al. / Journal of Quantitative Spectroscopy & Radiative Transfer ] (]]]]) ]]]–]]]

1

12 16

5

1

21112-01101

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3

, 10-3cm-1

2

, 10-3cm-1

7

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Miller et al (2004) Giver et al (2003) Toth et al (2006)

C O2

2

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20012-00001

3

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20013-00001

20011-00001

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Wavenumber, cm-1

17 19 21

4850

4900

4950

5000

5050

Fig. 3. Differences Δν between our observed line positions and those published by other authors for 12C16O2. Miller et al. (2004) – Ref. [16], Giver et al. (2003) – Ref. [17], Toth et al. (2006) – Ref. [18]. The large residuals for some weak lines are caused by their blending with the stronger lines.

Fig. 5. Differences Δν between our observed line positions and those published by Toth et al. [21] for 17O12C18O. The large residuals for the weak lines of the hot 21112–01101 band could be caused by blending of the lines in both Toth et al. [21] and our spectra.

16

25

8

27

33 35 37 39 41

Christensen et al (2012) Wang et al (2008) Toth et al (2007)

12 18

O C O

55 57

O C O

87 89

6

91

4

-2

95

-2

-4

-4

-6

-6

4700

93

0

4800

4900

5000

5100

97

4750

4800

4850

Fig. 4. Differences Δν between our observed line positions and those published by other authors for 16O12C18O. Christensen et al. (2012) – Ref. [19], Wang et al. (2008) – Ref. [20], Toth et al. (2007) – Ref. [21].

4900

4950

5000

5050

5100

Wavenumber, cm-1

Wavenumber, cm-1

61

53

Mandin (1977), Venus Mandin (1977), Mars

17

2

0

and Scalc are, respectively, the observed and where Sobs i i calculated values of the intensity for the ith line,

51

12

2

59

49

10

, 10-3cm-1

, 10-3cm-1

4

dipole moment operator are determined by the least squares fitting to the observed line intensities. The computer code used to fit the effective dipole moment parameters is described in Ref. [30]. Both our observed line intensities and those published in literature were used in the performed fits. Before in our research, the measurements of the line intensities in the considering wavenumber region were done only for two isotopologues, namely, 16O12C18O [21,31] and 17 12 18 O C O [21]. The eigenfunctions of the effective Hamiltonians published in Refs.[3,10,12] were used in the fits. The purpose of the fit is to minimize the value of the dimensionless standard deviation, χ, defined as vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi uP   2 u N obs calc =δi t i ¼ 1 Si
Si χ¼ ; ð3Þ N
n

47

16

8

6

43 45

81

85 12

10

31

79

83

23

29

77

Wavenumber, cm-1

101

Fig. 6. Differences Δν between our observed line positions and those published by Mandin [22] for 16O12C17O.

δi ¼ ðSobs i σ i Þ=100% is the absolute measurement error of ith line, σi is the measurement error in %, N is the number of fitted line intensities, and n is the number of adjusted effective dipole moment parameters. In the performed fits the accuracies declared by authors of the experimental sources were used for the weighting of measured data. For the description of the quality of a fit we use also the value of the root mean squares deviation defined according to the equation

RMS ¼

vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi uP   2 u N obs calc =Sobs t i ¼ 1 Si
Si i N

99

103 105 107 109 111 113 115

 100%:

ð4Þ

The characteristics of the input data and the results of the fits are presented in Table 3. The fitted sets of the effective dipole moment parameters are given in Table 4. As one can see from Table 3 an RMS of the fit for a given source is always within the measurement uncertainties.

Please cite this article as: Borkov YuG, et al. Infrared spectroscopy of 17O- and 18O-enriched carbon dioxide: Line positions and intensities in the 4681–5337 cm
1 region. J Quant Spectrosc Radiat Transfer (2015), http://dx.doi.org/10.1016/j. jqsrt.2015.02.019i

117 119 121 123

1

3

5

7

9

11

13

15

17

19

21

23

25

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33

35

37

39

41

43

45

47

49

51

53

55

57

59

61

6

StateðV 1 V 2 ℓ2 V 3 rεÞ

Gv

Bv

Dv  106

Hv  1012

O12C17O Fixed 02201e 02201f 01101e 01101f

1329.848065 1329.848065 1376.027327 1272.286470

0.380026 0.380026 0.378778 0.378699

0.13129 0.129826 0.107501 0.146378


0.298
0.016 0.0825 0.221

Fitted 30014e 30013e

6033.4761(1) 6175.9515(1)

0.37703970(5) 0.37498230(6)

0.1917(4) 0.1528(7)

0.7(2)

30012e

6298.1122(1)

0.37531270(4)

0.0889(3)

98/76

30011e 22213f 22213e 22212f 22212e 22211f 22211e

6463.4801(2) 6064.8394(2) 6064.8422(3) 6247.7031(1) 6247.7030(1) 6437.7206(2) 6437.7208(2)

0.37675580(8) 0.3776640(1) 0.3776350(2) 0.37695550(6) 0.37695570(6) 0.3772930(1) 0.3772980(1)

0.0699(8) 0.161(2) 0.104(2) 0.1331(5) 0.1350(5) 0.106(1) 0.148(1)

45/35 29/23 28/23 53/44 52/44 37/27 37/29

O12C18O Fixed 00001e 02201f 02201e 10001e 10002e

0.0 1319.818760 1319.818760 1355.654198 1244.594146

0.356931872 0.358277 0.358277 0.357407 0.356738

0.111566 0.115598 0.119470 0.097153 0.126339

Fitted 30013e 30012e 22212 01121e 01121f

6073.7606(1) 6207.7597(4) 6170.1277(3) 5255.4378(3) 5255.4379(2)

0.35331700(5) 0.3544170(2) 0.3555160(2) 0.3517870(2) 0.35227940(7)

0.1219(4) 0.087(4) 0.182(4) 0.119(3) 0.1153(6)

O12C17O Fixed 00001e 02201f 02201e 10001e 10002e

0.0 1324.536193 1324.536185 1364.940370 1258.235441

0.367195 0.368571 0.368571 0.367533 0.367124

0.118053 0.121885 0.124589 0.101728 0.136154

Fitted 30014e 30013e

5988.9128(1) 6122.70454(7)

0.36535020(4) 0.36352620(2)

0.1782(3) 0.1326(1)

50/42 79/62

30012e

6249.95050(9)

0.36432250(3)

0.0834(2)

62/45

30011e

6425.2070(2)

0.3656620(1)

0.059(2)

18/15

Ntot/ntota

Observed linesc

ΔGvb

Fitted bands

N/nd

RMSe

Notesf

16

Rothman1992 Rothman1992 Rothman1992 Rothman1992 54/46 98/88

30014e–10002e 30013e–10002e 30013e–10001e 30012e–10002e 30012e–10001e 30011e–10001e 22213f–02201f 22213e–02201e 22212f–02201f 22212e–02201e 22211f–02201f 22211e–02201e

4761.1896(1) 4903.6650(1) 4799.9242(1) 5025.8257(1) 4922.0849(1) 5087.4528(2) 4734.9941(3) 4734.9941(3) 4917.8550(1) 4917.8549(1) 5107.8727(2) 5107.8727(2)

P P P P P P P P P P P P

36/R 46/R 24/R 30/R 40/R 33/R 24/R 24/R 37/R 36/R 25/R 25/R

39 45 24 26 38 31 29 26 33 33 32 32

54/46 74/67 24/21 40/32 58/44 45/35 29/23 28/23 53/44 52/44 37/27 37/29

0.38 0.38 0.49 0.41 0.38 0.60 0.45 0.45 0.33 0.33 0.41 0.41

17

Claveau1998 Claveau1998 Claveau1998 Claveau1998 Claveau1998

0.049
0.245 0.232 0.201 51/33 20/15 10/8 18/11 27/22

30013e–10002e 30012e–10001e 22212e–02201e 01121e–00001e 01121f–00001e

4829.1665(1) 4852.1055(4) 4850.3089(3) 5255.4379(2) 5255.4379(2)

P 36/R 36 P 22/R 23 P 20/R 23 P 15/R 25 Q 35

51/33 20/15 10/8 18/11 27/22

0.47 0.30 0.65 0.52 0.52

&

17

Claveau1998 Claveau1998 Claveau1998 Claveau1998 Claveau1998


0.098
0.421 0.098 0.340 30014e–10002e 30013e–10002e 30013e–10001e 30012e–10002e 30012e–10001e 30011e–10001e

4730.6774(1) 4864.46910(7) 4757.76417(7) 4991.71506(9) 4885.01013(9) 5060.2666(2)

P P P P P P

35/R 45/R 23/R 21/R 37/R 27/R

39 45 22 27 39 27

50/42 65/55 14/7 10/5 52/40 18/15

0.29 0.39 0.44 0.23 0.39 0.60

Yu.G. Borkov et al. / Journal of Quantitative Spectroscopy & Radiative Transfer ] (]]]]) ]]]–]]]

Please cite this article as: Borkov YuG, et al. Infrared spectroscopy of 17O- and 18O-enriched carbon dioxide: Line positions and intensities in the 4681–5337 cm
1 region. J Quant Spectrosc Radiat Transfer (2015), http://dx.doi.org/10.1016/j. jqsrt.2015.02.019i

Table 2 Spectroscopic constants (cm
1) for the new observed bands of CO2.

63

65

67

69

71

73

75

77

79

81

83

85

87

89

91

93

95

97

99

101

103

105

107

109

111

113

115

1

3

5

38/30 36/24 19/13 17/11 56/42 37/34

7

9

P 32/R 35 P 29/R 35 P 16/R 22 P 16/R 22 P 33/R 34 Q 43

11

13

15

4882.2661(1) 4882.2661(1) 5077.1971(4) 5077.1971(4) 5273.8733(1) 5273.8733(1)

17

19

21

22212f–02201f 22212e–02201e 22211e–02201e 22211f–02201f 01121e–00001e 01121f–00001e

23

25

0.111130

38/30 36/24 19/13 17/11 56/42 37/34

27

0.356945

29

0.0

Fitted 20011e

31

O13C18O Fixed 00001e

33

0.1209(4) 0.1344(4) 0.103(4) 0.05(1) 0.1179(4) 0.1196(2)

35

0.36563180(5) 0.36563930(5) 0.3661020(2) 0.3660870(4) 0.36188330(4) 0.36240440(3)

37

6206.8029(1) 6206.8023(1) 6401.7322(3) 6401.7333(4) 5273.8731(1) 5273.8733(1)

39

41

43

45

47

49

51

53

55

57

59

61

0.43 0.43 0.41 0.41 0.40 0.40

17

4892.3914(2)

0.3546370(1)

0.080(1)

O13C17O Fixed 00001e

0.0

0.367212

0.11804

Fitted 20011e

4921.53176(9)

0.36456000(3)

0.0852(2)


0.18

Teffo1998 30/16

20011e–00001e

4892.3914(2)

P 28/R 29

30/16

0.47

17

Teffo1998 50/43

20011e–00001e

4921.53176(9)

P 39/R 39

50/43

0.28

Between parentheses, the confidence interval (1 SD) is in the units of the last quoted digit. a Ntot is the total number of the observed transitions reaching a given vibrational state and ntot is the number of them involved to the fit. b ΔGv ¼ G0v
G″v . c Observed branch with the maximum value of the total angular momentum quantum number. d N is the number of the observed lines for a given branch(es) and n is the number of these lines involved to the fit. e Root Mean Squares of residuals of the spectroscopic parameters fit is given in 10
3 cm
1. f Rothman1992 – Ref. [24], Claveau1998 – Ref. [25], Teffo1998 – Ref. [26]; “&” – unresolved doublets.

Table 3 Experimental input data and the results of the global line intensity fits for the ΔP ¼7 series of transitions in

16

O12C18O,

16

O12C17O,

12 17

C O2 ,

17

O12C18O,

16

O13C17O,

13 17

17

C O2 and

O13C18O.

Reference

Accuracy (%)

Nbanda

Nfitb

Nexcc

Npard

χ

RMS (%)e

16 12 18 O C O This work f Jacquemart et al. [1] Toth et al. [21] Durry et al. [31]

4.0–15.0 3.0 2.5–10 1.2

9

753 150 633 3

82 0 30 0

5

1.14

7.3 1.6 4.0 2.5

4.0–12.0 3.0

16

1289 189

139 0

7

1.07

6.1 1.6

4.0–12.0

15

1113

170

6

1.20

6.5

4.0–15.0 3.0 2.5–30

10

898 161 271

115 0 1

6

1.11

6.4 1.4 4.6

4.0–11.0

4

195

42

3

1.31

6.4

16

O12C17O This work Jacquemart et al. [1] 12 17

C O2 This work 17

Yu.G. Borkov et al. / Journal of Quantitative Spectroscopy & Radiative Transfer ] (]]]]) ]]]–]]]

Please cite this article as: Borkov YuG, et al. Infrared spectroscopy of 17O- and 18O-enriched carbon dioxide: Line positions and intensities in the 4681–5337 cm
1 region. J Quant Spectrosc Radiat Transfer (2015), http://dx.doi.org/10.1016/j. jqsrt.2015.02.019i

22212f 22212e 22211e 22211f 01121e 01121f

12 18

O C O This work Jacquemart et al. [1] Toth et al. [21] 16

O13C17O This work

7

63

65

67

69

71

73

75

77

79

81

83

85

87

89

91

93

95

97

99

101

103

105

107

109

111

113

115

117

119

121

123

1

3

5

7

9

11

13

15

17

19

21

23

25

27

29

31

33

35

37

39

41

43

45

47

49

51

53

55

57

59

61

8

C O2 This work 17 13 18 O C O This work

4.0–8.0

3

172

37

3

1.50

7.1

4.0–15.0

3

136

32

3

1.63

9.0

a

Nband – number of the involved bands. Nfit – number of lines of a given source included into the fit. c Nexc – number of lines of a given source excluded from the fit. d Npar – number of the adjusted parameters. e RMS – root mean squares of residuals for a given source. f This work – the majority of the line intensities is obtained in this work and small part of them is published in our paper [3]. b

Table 4 Effective dipole moment parameters for ΔP¼ 7 series of transitions of

16

O12C18O,

16

O12C17O,

12 17

C O2,

17

O12C18O,

16

O13C17O,

13 17

C O2 and

17

O13C18O.

ΔV1

ΔV2

ΔV3

Δℓ2

Value

a

Order

O C O M κ2 bJ M M

2 2 2 1 0

0 0 0 2 4

1 1 1 1 1

0 0 0 0 0


0.36652(27) 0.484(12) 0.151(20) 0.2916(11)
0.984(27)

10
2 10
2 10
3 10
3 10
5

O12C17O M bJ M M M M bJ

2 2 1 0 3 0 0

0 0 2 4 1 1 1

1 1 1 1 0 2 2

0 0 0 0 1 1 1


0.36861(26) 0.136(20) 0.2933(11)
0.1028(28)
0.119(17) 0.7843(21) 0.434(17)

10
2 10
3 10
3 10
4 10
4 10
4 10
3

2 2 1 0

0 0 2 4

1 1 1 1

0 0 0 0


0.35537(31) 0.134(25) 0.2794(14)
0.990(33)

10
2 10
3 10
3 10
5

Parameter 16

Yu.G. Borkov et al. / Journal of Quantitative Spectroscopy & Radiative Transfer ] (]]]]) ]]]–]]]

Please cite this article as: Borkov YuG, et al. Infrared spectroscopy of 17O- and 18O-enriched carbon dioxide: Line positions and intensities in the 4681–5337 cm
1 region. J Quant Spectrosc Radiat Transfer (2015), http://dx.doi.org/10.1016/j. jqsrt.2015.02.019i

13 17

12 18

16

12 17

C O2 M bJ M M

63

65

67

69

71

73

75

77

79

81

83

85

87

89

91

93

95

97

99

101

103

105

107

109

111

113

115

117

119

121

123

7


0.3484(13) 0.2599(87)
0.91(24)


0.35602(94) 0.2826(54)
0.108(16)

13

0.7745(28) 0.301(26)

11


0.35631(79) 0.2884(40)
0.80(12)


0.39365(26) 0.101(22) 0.3046(13)
0.1185(31) 0.8690(69) 0.493(91)

9

15 17 19

0 0 0

0 0 0

0 0 0

0 0 0 0 1 1

23

1 1

21

25 27 29

1 1 1

1 1 1

1 1 1

1 1 1 1 2 2

2 2

31 33 35 37

0 2 4

0 2 4

0 2 4

0 0 2 4 1 1

41

1 1

39

43 45 47

2 1 0

2 1 0

2 1 0

2 2 1 0 0 0

0 0

49 51 53 55

61

O13C18O M M M

17

C O2 M M M

13 17

O13C17O M M M

16

17

M bJ

59

O12C18O M bJ M M M bJ

57

9

7. Discussion and conclusion

63

Significant number of new observed line positions and intensities of 12 isotopologues of CO2 were obtained from the analysis of the Fourier Transform spectra of 17O enriched carbon dioxide in the region between 4681 and 5337 cm
1. In total 23 bands belonging to the ΔP ¼7 series of transitions in different isotopologues were newly assigned. The line positions and intensities for all observed bands were measured. Before this work the line intensities of the bands belonging to the ΔP¼ 7 series of transitions were extensively studied only for the three most abundant isotopologues: 12C16O2, 13C16O2 and 16O12C18O. As far as 16 12 17 O C O is concerned, the line intensities of the strongest triad 2001i–00001 (i¼1, 2, 3) were measured in our recent paper [1]. In the case of the 17O12C18O isotopologue only the 4 strongest bands were studied before [1,21] from 10 bands observed in this paper. One of the validations of the measured line intensities (or abundances of the isotopologues in our sample) is the comparison of the fitted effective dipole moment parameters. As it follows from [32] the isotopic substitution in carbon dioxide does not lead to considerable change of the effective dipole moment parameters in the case of the odd ΔP series of transitions. In Fig. 7 we have plotted the values of the third order M 2 0 1 and fourth order M 1 2 1 effective dipole moment parameters versus isotopologue. This figure shows that the residuals between the values of these parameters are within 6%. This could serve as confirmation (but only within 12% uncertainty) of the isotopologue abundances derived in our previous paper [1]. Even confirmation of the abundances with 12% uncertainty is important for the minor isotopologues 13C17O2 (0.27%) and 17O13C18O (0.11%) of our sample because their abundances were found using the statistics low. The line positions obtained in this paper were used for the refinement of the sets of the global effective Hamiltonians parameters for all stable isotopologues. The fitted effective Hamiltonian and effective dipole moment parameters were used to generate a new version of the CDSD databank [33].

65 67 69 71 73 75 77 79 81 83 85 87 89 91 93 95 97 99 101 103 105

Effective dipole moment parameter, Debye

5

a The parameters M are given in Debye while the κ2 and bJ parameters are dimensionless. Only relative signs of the M parameters within a given series of transitions are determined. The numbers in parentheses correspond to one standard deviation in units of the last quoted digit.

10
2 10
3 10
5

10
2 10
3 10
4

10
2 10
3 10
5

3

10
2 10
3 10
3 10
4 10
4 10
2

1

10
4 10
2

Yu.G. Borkov et al. / Journal of Quantitative Spectroscopy & Radiative Transfer ] (]]]]) ]]]–]]]

0.4

107 0.3

109

0.2 0.1

111 10 M

0.0

10 M

-0.1

113

-0.2

115

-0.3

117

-0.4

119 628

627

727

728

637

737

738

Fig. 7. Comparison of the effective dipole moment parameters M 2 0 1 and M 1 2 1 for different isotopologues. The presented error bars rely mostly on the uncertainties of the isotopologue abundances.

Please cite this article as: Borkov YuG, et al. Infrared spectroscopy of 17O- and 18O-enriched carbon dioxide: Line positions and intensities in the 4681–5337 cm
1 region. J Quant Spectrosc Radiat Transfer (2015), http://dx.doi.org/10.1016/j. jqsrt.2015.02.019i

121 123

10

1

Acknowledgements

3 Q2

5

Yu.G. Borkov et al. / Journal of Quantitative Spectroscopy & Radiative Transfer ] (]]]]) ]]]–]]]

This work is jointly supported by RFBR (Russia, Grants N 12-05-93106) and CNRS (France) in the framework of the Laboratoire International Associé Spectroscopie d’Absorption des Molécules d’Intérêt Atmosphérique (SAMIA).

7 Appendix A. Supporting information 9 11

Supplementary data associated with this article can be found in the online version at http://dx.doi.org/10.1016/j. jqsrt.2015.02.019.

13 15

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Please cite this article as: Borkov YuG, et al. Infrared spectroscopy of 17O- and 18O-enriched carbon dioxide: Line positions and intensities in the 4681–5337 cm
1 region. J Quant Spectrosc Radiat Transfer (2015), http://dx.doi.org/10.1016/j. jqsrt.2015.02.019i

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