1. Line list of HD 18 O rotation-vibration transitions for atmospheric applications Semen MIKHAILENKO, Olga NAUMENKO, and Sergei TASHKUN Laboratory of Theoretical Spectroscopy, V.E. Zuev Institute of Atmospheric Optics, 634021 Tomsk, RUSSIA An-Wen LIU and Shui-Ming HU Hefei National Laboratory for Physical Sciences at Microscale, University of Science and Technology of China, Hefei, 230026, CHINA The HD 18 O molecule was detected recently in the upper Earth’s atmosphere [1]. We present and discuss here a line list of HD 18 O aimed at atmospheric applications. Experimental transitions in the 0 - 11000 cm -1 region originating from different experimental sources [2-12] have been validated based on the theoretical computations by Partridge and Schwenke (PS) [13, 14] and the set of 3033 precise experimental energy levels has been obtained using the fundamental Rydberg-Ritz principle [15]. General information about presented line list and comparison with HITRAN data are presented in Tables 1 and 2. Our detailed and accurate line list of the HD 18 O rotation-vibration transitions has been constructed based on the experimental energy levels and PS intensities. Accuracy of line positions included into the line list is illustrated by Figs. 1 and 2, The ( OBS - CALC ) differences on Fig. 1 are given for a whole region considered. Differences for most accurate transitions with the declared experimental uncertainties not exceeding 0.0001 cm -1 are shown on Fig. 2. Quality of the PS intensities involved in the line list is confirmed by the comparisons with available experimental data which are shown on Figs. 3 and 4. HD 18 O line list for atmospheric applications has been constructed by scaling the PS intensities to the natural abundance ( 6.23x10 -7 according to [16]) and applying the intensity cutoff of 10 -30 cm/molecule at 296 K. A comparison of our line list and HITRAN data is given in Table 1. All variationally predicted HD 18 O lines important for evaluation of the solar radiation absorption by the Earth atmosphere are shown in Fig. 5 (upper panel); middle panel corresponds to total absorption due to HD 18 O transitions included into our line list; low panel represents residual absorption. The calculated absorption spectra of the atmospheric air with (upper panel) and without (middle panel) contribution from water vapor, and HD 18 O (lower panel) in 0-8800 cm -1 spectral range are given in Fig. 6. Contribution of the HD 18 O absorption lines is clearly seen in the region of rotational bands and near 1500 and 3900 cm -1. Fig. 5. Atmospheric absorption with (upper panel) and without (middle panel) water vapor. Lower panel – absorption of HD 18 O References 1. Z. Zelinger et al., Molecular Physics, 104 (2006) 2815-2820. 2. G. Steenbeckeliers,Private communication (July 1971). 3. J.W. Fleming, M.J. Gibson, J. Mol. Spectrosc. 62 (1976) 326-337. 4. J.W.C. Johns, JOSA, B2 (1985) 1340-1354. 5. R.A. Toth, J. Mol. Spectrosc. 162 (1993) 20-41. 6. R.A. Toth, J. Mol. Spectrosc. 198 (1999) 358-370. 7. R.A. Toth, J. Mol. Structure, 742 (2005) 49-68. 8. A.-W. Liu et al., J. Mol. Spectrosc. 237 (2006) 149-162. 9. F. Mazzotti et al., J. Mol. Spectrosc. 243 (2007) 78-89. 10. S.N. Mikhailenko et al., JQSRT, 110 (2009) 597-608. 11. A.-W. Liu et al., JQSRT, 110 (2009) 1781-1800. 12. O.V. Naumenko et al., JQSRT, 111 (2010) 36-44. 13. H. Partridge, D.W. Schwenke, J. Chem. Phys. 106 (1997) 4618-4639. 14. D.W. Schwenke, H. Partridge, J. Chem. Phys. 113 (2000) 6592-6597. 15. S.N. Mikhailenko et al., Oral FA06 on 65 th OSU Symposium, Columbus, OH, USA, June 21-25, 2010 16. L.S. Rothman et al., JQSRT, 110 (2009) 533-572. Fig. 6. PS calculated (upper panel), predicted from experimental energies (middle panel) and their difference for the line positions of HD 18 O Table 1. General comparison of our and HITRAN line lists Our line listHITRAN Spectral Region (cm -1 )8 – 10 6890.017 – 3825 Number of Transitions58951611 Cut-off (cm/molecule)1x10 -30 2x10 -34 *), 2x10 -27 Number of Bands184 J max, K a max 20, 1113, 9 *) Only for pure rotational band Band Number of Transitions Region / cm -1 (000) – (000) 9868 – 668 (010) – (010) 12043 – 329 (010) – (000)11051036 – 1834 (020) – (010) 761248 – 1496 (100) – (000) 5052465 – 2992 (020) – (000) 3992591 – 3160 (001) – (000) 9593312 – 3984 (110) – (000) 2613921 – 4344 (030) – (000) 1523971 – 4311 (011) – (000) 4254857 – 5348 (200) – (000) 1875144 – 5463 (040) – (000) 25285 – 5333 (101) – (000) 1046215 – 6575 (021) – (000) 376348 – 6538 (210) – (000) 156650 – 6786 (002) – (000) 4556926 – 7434 (012) – (000) 788471 – 8702 (003) – (000) 2910 525 – 10 689 Table 2. Overview of our line list Fig. 1. Deviations of observed ( OBS ) and calculated ( CALC ) line positions for the whole spectral region Fig. 2. Deviations of observed ( OBS ) and calculated ( CALC ) wavenumbers for precise line positions (with uncertainties not exceeding 0.0001 cm -1 ) Fig. 3. I OBS / I PS intensity ratio for the line intensities of the 2 band [5]. Fig. 4. I OBS / I PS intensity ratio for the line intensities in the 6000-9200 cm -1 region. Calculation conditions for Fig. 5 Pressure – 1 atm Path – 1200 m Apparatus resolution – 0.01 cm -1 Apparatus function – SINC**2 Temperature – 296 K Gas mixture: Water – 1.863% Carbon dioxide – 0.0327% Ozone – 3  10 -6 % Nitrous oxide – 3.2  10 -5 % Carbon monoxide – 1.5  10 -5 % Methane – 1.68  10 -4 % Oxygen – 20.711% Nitrogen – 77.393%