Egorov, Oleg V.

Kashirskii, Danila E.

Voitsekhovskaya, Olga K.

English

Tomsk State University Repository

ИЗВЕСТИЯ ВЫСШИХ УЧЕБНЫХ ЗАВЕДЕНИЙТ. 55, № 8/3 ФИЗИКА 2012УДК 535.343.4O.K. VOITSEKHOVSKAYA, O.V. EGOROV, D.E. KASHIRSCIYABSORPTION AND RADIATION PROPERIES OF THE SULFUR-CONTAININGGASEOUS COMPOUNDS1We report the scheme of calculating spectral line parameters (PSL) for hydrogen sulfide (H2S) and sulfur dioxide(SO2) gases based on the algorithm of calculating PSL for the asymmetric type molecules. The peculiarity of the proce-dure is the need to calculate the large volumes of PSL as the investigation temperature range 300-1200 (K)) imposes thecertain demands on the maximum values of the quantum numbers of vibration – rotation (VR) states. With the tempera-ture growth the populations of the “hot” transition levels are increased and, accordingly, the all higher VR states must beincluded in calculation process. Derived by calculation the intensities and the wavenumber of absorption lines of SO2 andH2S were used for finding the absorption coefficient and emissivity of these gases with parallel analysis of the contribu-tions of every vibrational band in the total band intensity.Keywords: hydrogen sulfur, sulfur dioxide, absorption coefficient, emissivity.The data of PSL of the hydrogen sulfur and sulfur dioxide molecules are an important for solving theproblems of controlling the concentration these gases in the Earth’s atmosphere and in astrophysical ap-plications. The traditional approach of describing the spectrum of asymmetric type molecules based onthe effective VR Hamiltonian. Generally the corresponding VR Hamiltonian has the form of block diago-nal matrix [1]:', '' ,PH Hυυυ υ ∈= υ υ∑which consists of the polyad of interacting vibrational states, selected by the following rules: 2υ1+υ2+2υ3 == P = 1, 2, 3, …, where  υ1, υ2, and υ3 – vibrational quantum numbers.According to the formalism proposed in the work [2] the computer program for obtaining the energyof VR levels with an accounting of non-diagonal operators has been created and the calculations of thespectra of investigation gases have been made.The Fig.1a presents the absorption coefficient of SO2 in the terahertz range (1–250 cm–1) at differenttemperatures with the wavenumber spectral intervals of v∆ =10 cm–1. It can be seen that with the growthof the temperature the number of the “hot” transitions increase which leads to decreasing the absorptioncoefficient in the center of band and to its shifting to the more high wavenumbers. At normal conditions(T = 300 K, P = 1 atm) the strongest absorption transitions belong to (000-000) band but at high tem-perature the total value depends on transitions within the other bands. Particularly the contribution of(010–010) band enlarges from 7.7 % at T = 300 K to 20.8 % at T = 900 K (table 1).     Fig. 1. Temperature dependence of the absorption coefficient (a) and emissivity (b) ofSO2 molecule in the range 1 – 250 cm–1: 1 – 300 K; 2 – 600 K; 3 – 900 K; 4 – 1200 K.The line intensity for the pure rotational transition was determined by the method, described in detailin [3] but in the formula (1) we used the VR partition sum instead of rotational and as HITEMP [4] the                                                     1 The work was supported by President grant 512.2012.2 and Federal Special-Purpose Programme “Scientific and scientific-educational personnel of innovation Russia” project No. 02.740.11.0562.а b1234123 4O.K. Voitsekhovskaya, O. V. Egorov, D.E. Kashirsciy222temperature coefficient T/To didn’t take into account. The constant of permanent dipole moment (μo) wasequal 1.6331 D [5].The emissivity (Fig.1b) was got according to [6] with the partial pressure (ρ) equal 1 atm and thelength of a trace (L ) –1 m.The Fig.2 demonstrates the absorption coefficient (a) and emissivity (b) of H2S molecule corre-sponding to the fundamental transitions (000-000) at T = 300 K, ρ=1 atm-1 and L=1 m. The calculationwere carried out with μo = 0.974 D [7] and the set of parameters of the Hamiltonian from [8].            Fig.2. Absorption coefficient (a) and emissivity (b) of H2S molecule corresponding tothe fundamental transitions (000-000) at T = 300 K.T a b l e  1The estimation of contribution of the fundamental bands to the total absorption coefficientof the SO2 molecule000-000 010-010 001-001 100-100 020-020 011-011 110-110 030-030Band,  υ1υ2υ3-υ1υ2υ3 [9] [10] [11]300 KO 90.9 7.7 0.13 0.36 0.66 1.13 ⋅ 10-2 3.12 ⋅ 10-2 5.59 ⋅ 10-2600 KO 64.6 19 2.36 3.95 5.42 0.68 1.14 1.56900 KO 46.6 20.8 4.64 6.56 8.24 1.91 2.7 3.40Relative con-tribution*, %1200 KO 37.3 20.5 5.73 7.46 9 2.77 3.61 4.36* TS 100%/ Snii∑ ⋅ , TS  – integrated intensity at given temperature T, Snii∑  – sum of intensities of the rotational transi-tions within the band; n – number of the lines in the band; [] – source of the constants of the Hamiltonian whichwere used in calculation.In the current work, we presented the results of calculating the PSL of sulfur-containing gaseouscompounds, corresponding to the rotational transitions. These data can be used as the reference in the ac-tive and passive methods of the remote sounding in the terahertz range of electromagnetic waves.REFERENCES1. Б ы к о в  А . Д . ,  М а к у ш к и н  Ю . С . ,  У л е н и к о в  О . Н . Колебательно-вращательная спектроскопия во-дяного пара. – Новосибирск: Наука, 1989. – 296 с.2. K w a n  Y . Y .  // J. Mol. Spectrosc. – 1978. – V. 71. – P. 260–280.3. P i c k e t  H . M . ,  C o h e n  E . A . ,  D r o u i n  B . J . ,  a n d  P e a r s o n  J . C . Submillimeter, millimeter, and mi-crowave spectral line catalog NASA/JPL, Online version: http://spec.jpl.nasa.gov/ftp/pub/catalog/doc/catdoc.pdf.4. http://www.cfa.harvard.edu/hitran.5. P a t e l  D . ,  M a r g o l e s e  D . ,  a n d  D y k e  T . R .  //J. Chem. Phys. – 1979. – No. 2740. – V. 70.6. П е н н е р  С . С .  // Количественная молекулярная спектроскопия и излучательная способность газов. – М.: ИЛ,1963. – 495 с.7. H u i s z o o n  C .  a n d  D y m a n u s  A .  // Physica. – 1965. – V. 31. – P. 1049–1052.8. F l a u d  J . - M . ,  C a m y - P e y r e t  C . ,  a n d  J o h n s  J . W . C .  // Can. J. Phys. – 1983. – V. 61. – P. 1462–1473.9. H o l d e r  M ϋ l l e r  S . P .  a n d  B r ϋ k e n  S .  // J. Mol. Spectrosc. – 2005. – V. 232. – P. 213–222.10. F l a u d  J . - M . ,  P e r r i n  A . ,  S a l a h  L . M . ,  e t  a l .  // J. Mol. Spectrosc. – 1993. – V. 160. – P. 272–278.11. U l e n i k o v  O . N . ,  G r o m o v a  O . V . ,  B e k h t e r e v a  E . S . ,  e t  a l . // JQSRT. – 2011. – V. 112. – P. 486–512.Tomsk State University, Tomsk, Russia Поступила в редакцию 15.06.12.E-mail: vok@elefot.tsu.ru_______________Войцеховская Ольга Кузьминична, д.ф.-м.н., профессор;Егоров Олег Викторович, студент;Каширский Данила Евгеньевич, аспирант.а b

Absorption and radiation properies of the sulfur-containing gaseous compounds

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Absorption and radiation properies of the sulfur-containing gaseous compounds

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