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

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, (2006) - HITRAN 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 ( – cm -1 ) // J. Mol. Spectrosc. 243, (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, (1999) - mass-depended PES of the water molecule

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 cm -1

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

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, (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: /j.jqsrt

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 – cm -1 Resolution (1/MOPD): – 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 cm -1 region // J. Mol. Spectrosc. 237, (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, (2008)

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

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 – cm -1 More details: S.N. Mikhailenko et al., JQSRT, 110, (2009) S.N. Mikhailenko et al., JQSRT (2010) doi: /j.jqsrt 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, (2009) O.V. Naumenko et al., JQSRT, 111, (2010)

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

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

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, (1997) D.W. Schwenke and H. Partridge, J. Chem. Phys. 113, (2000) Calculated line lists are available at

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 cm -1

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

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

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

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

Levels of HD 18 O and D 2 18 O Line positions: Comparison of observed line positions of the band of D 2 18 O with PS prediction

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

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 of RFBR (Russia) and NNSF (China) - Grant No of RFBR (Russia) and NNSF (China) - Grant No. RUG TO-09 of CRDF (USA) and RFBR (Russia) - Program 3.9 “Fundamental Optical Spectroscopy and Applications” of RAS