1. Experimental Energy Levels of HD 18 O and D 2 18 O S.N. MIKHAILENKO, O.V. NAUMENKO, S.A. TASHKUN Laboratory of Theoretical Spectroscopy, V.E. Zuev Institute of Atmospheric Optics,Tomsk, RUSSIA A.-W. LIU and S.-M. HU Hefei National Laboratory for Physical Science at Microscale, University of Science and Technology of China, Hefei, CHINA

2. Levels of HD 18 O and D 2 18 O Motivation 1. Atmospheric applications - Z. Zelinger et al., Observation of HD 18 O, CH 3 OH and vibrationally-excited N 2 O from Odin/SMR measurements // Molecular Physics, 104, 2815-2820 (2006) - HITRAN-2008 2. Astrophysical applications - ALMA and Hershel apparatus need “Accurate line frequencies up to 2 THz of all molecules & their isotopic species & their vibrationally excited states” Prof. Jose Cernicharo, Invited talk on the HighRus-2009 symposium 3. Spectroscopy - analysis of the water spectra (HD 18 O and D 2 18 O species have been found without special enrichment) F. Mazzotti, R.N. Tolchenov, A. Campargue, High sensitivity ICLAS of H 2 18 O in the region of second decade (11 520 – 12 810 cm -1 ) // J. Mol. Spectrosc. 243, 78-89 (2007) R.A. Toth, Air- and N 2 -broadening parameters of HDO and D 2 O, 709 to 1936 cm -1 // J. Mol. Spectrosc. 198, 358-370 (1999) - mass-depended PES of the water molecule

3. Levels of HD 18 O and D 2 18 O Previous studies HD 18 O: about 1320 transitions have been measured between 0 and 3020 cm -1 and 93 transitions around 12000 cm -1

4. Levels of HD 18 O and D 2 18 O Previous studies D 2 18 O: about 1200 transitions have been measured below 2920 cm -1

5. Levels of HD 18 O and D 2 18 O Previous studies Current status of the HD 18 O and D 2 18 O spectra studies is given in -S.N. Mikhailenko, S.A. Tashkun, T.A. Putilova, E.N. Starikova, L. Daumont, A. Jenouvrier, S. Fally, M. Carleer, C. Hermans, A.C. Vandaele, Critical evaluation of measured rotation-vibration transitions and an experimental dataset of energy levels of HD 18 O // JQSRT, 110, 597-608 (2009) - S.N. Mikhailenko, S.A. Tashkun, L. Daumont, A. Jenouvrier, M. Carleer, S. Fally, A.C. Vandaele, Line positions and energy levels of the 18 O substitutions from the HDO/D 2 O spectra between 5600 and 8800 cm -1 // JQSRT (2010) doi:10.1016/j.jqsrt.2010.01.028

6. Levels of HD 18 O and D 2 18 O New measurements I. The USTC absorption spectra measurements of the water vapor enriched by oxygen-18 and deuterium Instrument: Bruker IFS 120 HR with a 1-m base length multi-pass gas cell Spectral region: 950 – 11 000 cm -1 Resolution (1/MOPD): 0.005 – 0.015 cm -1 Temperature: room Path length: 15, 35 and 105 m Pressure: 11 – 1935 Pa More details: A.-W. Liu, J.-H. Du, K.-F. Song, L. Wang, L. Wan, S.-M. Hu, High-resolution Fourier- transform spectroscopy of 18 O-enriched water molecule in the 1080-7800 cm -1 region // J. Mol. Spectrosc. 237, 149-162 (2006) N.-Y. Ni, A.-W. Liu, K.-F. Song, S.-M. Hu, O.V. Naumenko, T.V. Kruglova, S.A. Tashkun, High-resolution spectroscopy of the triple-substituted isotopologue of water molecule D 2 18 O: the first triad // Molecular Physics, 106, 1793-1801 (2008)

7. Levels of HD 18 O and D 2 18 O Overview of the absorption spectrum in the 6000–9200 cm -1, P=1935 Pa, L=35 m

8. Levels of HD 18 O and D 2 18 O New measurements II. Reims-Bruxelles long-path FTS measurements of water vapor spectra Instrument: Bruker IFS 120 HR with a 50-m base length multi-pass gas cell Spectral region: 4200 – 11 600 cm -1 More details: S.N. Mikhailenko et al., JQSRT, 110, 597-608 (2009) S.N. Mikhailenko et al., JQSRT (2010) doi:10.1016/j.jqsrt.2010.01.028 III. ICLAS and CW-CRDS measurements of water vapor spectra Instrument: ICLAS and CW-CRDS spectrometers (LSP, Grenoble) Spectral region: 1.6 and 0.71  m More details: A. Liu et al., JQSRT, 110, 1781-1800 (2009) O.V. Naumenko et al., JQSRT, 111, 36-44 (2010)

9. Levels of HD 18 O and D 2 18 O New measurements HD 18 O: more than 14 000 transitions between 990 and 14 000 cm -1

10. Levels of HD 18 O and D 2 18 O New measurements D 2 18 O: about 10 400 transitions between 970 and 9110 cm -1

11. Levels of HD 18 O and D 2 18 O Spectra analysis Spectroscopic assignment of the observed lines: H 2 17 O, H 2 16 O, H 2 18 O, HD 16 O, and D 2 16 O species – trivial assignment using known energy levels HD 18 O and D 2 18 O molecules – assignment using theoretical line lists based on the results of H. Partridge and D.W. Schwenke, J. Chem. Phys. 106, 4618-4639 (1997) D.W. Schwenke and H. Partridge, J. Chem. Phys. 113, 6592-6597 (2000) Calculated line lists are available at http://spectra.iao.ru http://spectra.iao.ru

12. Levels of HD 18 O and D 2 18 O Spectra analysis Calculated spectra of HD 18 O (upper panel) and D 2 18 O (lower panel) in the 6600-9200 cm -1

13. Levels of HD 18 O and D 2 18 O Spectra analysis: Example of the HD 18 O/D 2 18 O absorption near 7714 cm -1

14. Levels of HD 18 O and D 2 18 O more than new 3100 levels of 32 vibrational states up to 14 686 cm -1 HD 18 O Energy levels: Previously known levels are in green, new levels are in red

15. Levels of HD 18 O and D 2 18 O about 3600 new levels of 24 vibrational states up to 9775 cm -1 D 2 18 O: Energy levels: Previously known levels are in green, new levels are in red

16. Levels of HD 18 O and D 2 18 O Line positions: Comparison of observed line positions of HD 18 O (upper panel) and D 2 18 O (lower panel) with theoretical (PS) predictions

17. Levels of HD 18 O and D 2 18 O Line positions: Comparison of observed line positions of the 1 + 2 + 3 band of D 2 18 O with PS prediction

18. Levels of HD 18 O and D 2 18 O Conclusion: -More than 14 000 transitions of HD 18 O have been assigned in the 990 – 14000 cm -1 spectral range. Transitions of 26 upper vibrational states where observed for the first time. -About 10 400 transitions of D 2 18 O have been assigned in the 970 – 9110 cm -1 spectral range. Transitions of 21 upper vibrational states where observed for the first time. -Number of HD 18 O experimental energy levels has been extended from 532 up to 3114. -Number of D 2 18 O experimental energy levels has been extended from 532 up to 3598.

19. Levels of HD 18 O and D 2 18 O Acknowledgments: CHINARUSSIA H.-Y. Ni O. Leshchishina K.-F. Song T. Putilova J.-H. Du E. Starikova L. Wang I. Vasilenko L. Wan FRANCEBELGIUM A. CampargueM. Carleer S. Kassi S. Fally A. Jenouvrier A.C. Vandaele L. Daumont Financial support: - Grant No. 06-03-39014 of RFBR (Russia) and NNSF (China) - Grant No. 10-05-91176 of RFBR (Russia) and NNSF (China) - Grant No. RUG1-2954-TO-09 of CRDF (USA) and RFBR (Russia) - Program 3.9 “Fundamental Optical Spectroscopy and Applications” of RAS