Experimental Energy Levels of HD18O and D2

18O

S.N. MIKHAILENKO, O.V. NAUMENKO, S.A. TASHKUNLaboratory 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 HD18O and D218O

Motivation

1. Atmospheric applications

- Z. Zelinger et al., Observation of HD18O, CH3OH and vibrationally-excited N2O 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 (HD18O and D218O species have been found without special enrichment)

F. Mazzotti, R.N. Tolchenov, A. Campargue, High sensitivity ICLAS of H218O in the region of second

decade (11 520 – 12 810 cm-1) // J. Mol. Spectrosc. 243, 78-89 (2007)

R.A. Toth, Air- and N2-broadening parameters of HDO and D2O, 709 to 1936 cm-1 // J. Mol. Spectrosc.

198, 358-370 (1999)

- mass-depended PES of the water molecule

Levels of HD18O and D218O

Previous studies

HD18O: about 1320 transitions have been measured between 0 and 3020 cm-1 and 93

transitions around 12000 cm-1

0 2000 4000 6000 8000 10000 12000 14000

R. Toth, FT, JMStru (2005)

F. Mazzotti et al., ICLAS, JMS (2007)

R. Toth, FT, JMS (1993)

J.W.C. Johns, FT, JOSA B (1985)

J.W. Fleming & M.J. Gibson, FT, JMS (1976)

G. Steenbeckeliers, MW (1971)cm-1

JPL HITRAN-2008

Levels of HD18O and D218O

Previous studies

D218O: about 1200 transitions have been measured below 2920 cm-1

0 2000 4000 6000 8000 10000

R. Toth, FT, JMStru (2005)

G. Di Lonardo & L. Fusina, FT, JMS (1989)

R. Toth, FT, JMS (1993)

W. Wang et al., FT, JMS (1996)

J.W.C. Johns, FT, JOSA B (1985)

J.W. Fleming & M.J. Gibson, FT, JMS (1976)

J. Bellet et al., MW, JMS (1973)cm-1

Levels of HD18O and D218O

Previous studies

Current status of the HD18O and D218O 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 HD18O // 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 18O substitutions from the HDO/D2O

spectra between 5600 and 8800 cm-1 // JQSRT (2010) doi:10.1016/j.jqsrt.2010.01.028

Levels of HD18O and D218O

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 18O-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

D218O: the first triad // Molecular Physics, 106, 1793-1801 (2008)

Levels of HD18O and D218O

6000 6500 7000 7500 8000 8500 9000

0.0

0.2

0.4

0.6

0.8

1.0

cm-1

Transmittance

Overview of the absorption spectrum in the 6000–9200 cm-1, P=1935 Pa, L=35 m

Levels of HD18O and D218O

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)

0 2000 4000 6000 8000 10000 12000 14000

O. Naumenko et al., ICLAS, JQSRT (2010)

A. Liu et al., CW-CRDS, JQSRT (2009)

S. Mikhailenko et al., FT, JQSRT (2009)

R. Toth, FT, JMStru (2005)

F. Mazzotti et al., ICLAS, JMS (2007)

R. Toth, FT, JMS (1993)

J.W.C. Johns, FT, JOSA B (1985)

J.W. Fleming & M.J. Gibson, FT, JMS (1976)

G. Steenbeckeliers, MW (1971)cm-1

JPL HITRAN-2008

USTC data

Levels of HD18O and D218O

New measurements

HD18O: more than 14 000 transitions between 990 and 14 000 cm-1

Levels of HD18O and D218O

New measurements

D218O: about 10 400 transitions between 970 and 9110 cm-1

0 2000 4000 6000 8000 10000

R. Toth, FT, JMStru (2005)

G. Di Lonardo & L. Fusina, FT, JMS (1989)

R. Toth, FT, JMS (1993)

W. Wang et al., FT, JMS (1996)

J.W.C. Johns, FT, JOSA B (1985)

J.W. Fleming & M.J. Gibson, FT, JMS (1976)

J. Bellet et al., MW, JMS (1973)cm-1

S. Mikhailenko, FT, JQSRT (2010)

USTC data

Levels of HD18O and D218O

Spectra analysis

Spectroscopic assignment of the observed lines:

H217O, H2

16O, H218O, HD16O, and D2

16O species – trivial assignment using known energy

levels

HD18O and D218O 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

Levels of HD18O and D218O

Spectra analysis

Calculated spectra of HD18O (upper panel) and D218O (lower panel) in the 6600-9200 cm-1

Levels of HD18O and D218O

Spectra analysis:

Example of the HD18O/D218O absorption near 7714 cm-1

7711 7712 7713 7714 7715 7716

0.4

0.5

0.6

0.7

0.8

0.9

1.0

282262282

Transmittance

182

182182282

282

282

282

262262182182

182

282

282

282

282

282

282

182

182182

cm-1

182

282

Levels of HD18O and D218O

more than new 3100 levels of 32 vibrational states up to 14 686 cm-1

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32

0

3000

6000

9000

12000

15000

(003)

(004)

(013)

(400)(022) (102)

(310) (070)(201) (041) (121)

(012)

(031) (111) (060) (300)

(002)

(050) (210) (130)(101) (021)

(040)

(200)(011)

(110) (030)(001)

(100) (020)

Energy / cm-1

Ranking number of vibrational state

(010)

HD18O Energy levels:

Previously known levels are in green, new levels are in red

Levels of HD18O and D218O

about 3600 new levels of 24 vibrational states up to 9775 cm-1

0 2 4 6 8 10 12 14 16 18 20 22 24

0

2000

4000

6000

8000

10000

(310)(211)

(003)(102)

(022)(201)(300)(121)(220)

(041)

(012)(111)(210)

(100)

(000)

(112)

(030)

(031)

(020)

(110) (011)

(130)

(001)

Energy / cm-1

Ranking number of vibrational state

(010)

D218O: Energy levels:

Previously known levels are in green, new levels are in red

Levels of HD18O and D218O

Line positions:

Comparison of observed line positions of HD18O (upper panel) and D218O (lower

panel) with theoretical (PS) predictions

2000 4000 6000 8000 10000 12000 14000

-400

-300

-200

-100

0

100

200

300 2000 4000 6000 8000 10000 12000 14000

-400

-300

-200

-100

0

100

200

300

OB

S -

PS /

10-3 c

m-1

Wavenumber / cm-1

Levels of HD18O and D218O

Line positions:

Comparison of observed line positions of the 1+2+3 band of D218O with PS prediction

6200 6300 6400 6500 6600 6700 6800

-200

-150

-100

-50

0

50

100

150

200 OBS - PS / 10-3 cm-1

Wavenumber / cm-1

Levels of HD18O and D218O

Conclusion:

- More than 14 000 transitions of HD18O 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 D218O 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 HD18O experimental energy levels has been extended from 532 up to

3114.

- Number of D218O experimental energy levels has been extended from 532 up to

3598.

Levels of HD18O and D218O

Acknowledgments:

CHINA RUSSIAH.-Y. Ni O. LeshchishinaK.-F. Song T. PutilovaJ.-H. Du E. StarikovaL. Wang I. VasilenkoL. Wan

FRANCE BELGIUM A. Campargue M. CarleerS. Kassi S. FallyA. Jenouvrier A.C. VandaeleL. 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