The IUPAC water vapour database Jonathan Tennyson HITRAN

The IUPAC water vapour database Jonathan Tennyson HITRAN meeting Department of Physics and Astronomy Harvard University College London June 2008

A Database of Water Transitions from Experiment and Theory Members: Jonathan Tennyson (chair), P. F. Bernath, A. Campargue, M. R. Carleer, A. G. Császár, R. R. Gamache, J. Hodges, (A. Jenouvrier), O. Naumenko, O. L. Polyansky, L. S. Rothman, R. A. Toth, A. C. Vandaele, N. F. Zobov L Brown, L Daumont Objective: Develop a compilation of experimental and theoretical line positions, energy levels, intensities, and line-shape parameters for water vapour and all of its major isotopologues Establish a database structure that retains and enables access to all critically evaluated data

IUPAC Task group Database (W@DIS) in parts: 1. Energy levels and frequencies (MARVEL): progress update 2. Line intensities is best way forward ab initio? 3. Pressure dependence Gamache et al 4. Archive: experimental data and calculated linelists. Alex Fazliev Will use: • multiple data sources for each region • back filled by theory

“Water continuum”: Anomalous Features • 6. 4*1019 molecules cm-3 • T = 95 C • All fitting parameters (except water database) identical for both cases. ‘Continuum Feature’ (HITRAN) No feature (UCL) A. J. L. Shillings and R. L. Jones, University of Cambridge

Iodine Measurements • Iodine released by certain seaweeds when under stress (low tide). • Emitted I 2 leads to significant aerosol production and has an impact on ozone chemistry. • Need accurate I 2 measurements to better understand detailed mechanisms involved. • Retrieved I 2 and NO 2 concentrations depend on the water database employed. • Disagreement for I 2 up to ± 20 ppt, (which is chemically significant), NO 2 disagreement up to ± 0. 65 ppb (UCL 08 gives better agreement with independent chemiluminescence NO 2 measurements). A. J. L. Shillings, S. M. Ball and R. L. Jones, University of Cambridge Measurements performed during RHa. MBLe campaign, Roscoff, France, 2006.

MARVEL: inverse, experimental rovibrational energy levels Measured Active Rotational-Vibrational Energy Levels Based on: 1. X-matrix protocol of Flaud et al (1976) applied to all spectra 2. Relatively robust error method of Watson T. Furtenbacher, A. G. Császár, J. Tennyson, J. Mol. Spectrosc. 245, 115 (2007) T. Furtenbacher, A. G. Császár, J. Quant. Spectr. Rad. Transfer 109, 1234 (2008)

Observed transition wavenumbers ij with assignments and uncertainties The ij can be determined by term values Ei, Ej, . . Assignment i, j ij . . . +1. . . -1. . . . = × . . Ei . . Ej = X × E Solve for E (least-squares with experimental uncertainties of the ij) obtain experimentally derived term values Ei, Ej, . .

Spectroscopic networks of water Water (except for HDO) has two main SNs: (Ka + Kc + n 3) is even (Ka + Kc + n 3) is odd (para) (ortho) „magic number”

MARVEL steps (1) Collect, validate, and compile all available measured transitions, including their systematic and unique assignments and uncertainties, into a single database. (2) Based on the given database of assigned transitions, determine those energy levels of the given species which belong to a particular spectroscopic network (SN). (3) Cleansing of the database (misassignments, mislabelings). (4) Within a given SN, set up a vector containing all the experimentally measured transitions selected, another one comprising the requested measured energy levels, and a design matrix which describes the relation between the transitions and the energy levels. (5) Solve the resulting set of linear equations corresponding to the chosen set of vectors and the inversion matrix many times (robust reweighting). During solution of the set of linear equations uncertainties in the measured transitions can be incorporated which result in uncertainties of the energy levels determined.

Input database Freq/cm-1 unc. /10 -6 cm-1 assignment unique label other info 0. 30077226 0. 31558743 0. 31723578 0. 34827138 0. 75701556 0. 768572325 0. 80647272 0. 872355105 1. 261732005 1. 701219744 2. 161459377 2. 217844602 … 0. 7659 4. 5621 2. 2311 0. 1998 3. 0969 0. 7326 13. 9194 0. 999 1. 5318 0. 666 1. 3653 1. 0656 000 7 4 3 000 10 5 5 000 3 2 1 000 2 2 0 000 7 1 7 000 5 3 2 000 11 5 6 000 8 4 4 000 4 3 1 000 3 2 1 000 9 4 5 000 6 3 3 000 7 4 4 000 10 5 6 000 4 1 4 000 2 2 1 000 6 2 4 000 5 3 3 000 11 5 7 000 8 4 5 000 5 2 4 000 3 2 2 000 9 4 6 000 6 3 4 83 Johns. 1 83 Johns. 2 83 Johns. 3 83 Johns. 4 83 Johns. 5 83 Johns. 6 83 Johns. 7 83 Johns. 8 83 Johns. 9 83 Johns. 10 83 Johns. 11 83 Johns. 12 Java-based test facility: http: //theop 11. chem. elte. hu/marvel/MARVEL_JAVACODE. html

Home H 216 O H 2 16 O Data Manager : Jonathan Tennyson Number of MARVEL levels : Number of measured transitions : (UC) H 217 O H 218 O (UC) HD 16 O HD 17 O Marvel web page: http: //chaos. chem. elte. hu/marvel/ H O HD 18 O D 216 O (UC) D 217 O (UC) 17 2 Data Manager : Tibor Furtenbacher & Attila G. Császár Number of MARVEL levels : 2 736 Number of measured transitions : 8 424 D 218 O (UC) MARVEL levels and transitions Details >>> UPLOAD (UC) H 218 O Data Manager : Nikolai Zobov Number of MARVEL levels : Number of measured transitions :

Observed Transitions of H 217 O Interval (cm-1) References 1. 0 - 170 J. Steenbeckeliers, CRAS Paris B 273 (1971) 471 2. 0 - 170 F. C. De Lucia, J. Mol. Spectrosc. 56 (1975) 138 - 145 PDF 3. 0 - 177 F. Matsushima, H. Nagase, T. Nakauchi, H. Odashima, and K. Takagi, J. Mol. Spectrosc. 193 (1999) 217 – 223 PDF 4. 177 - 600 J. Kauppinen and E. Kyro, J. Mol. Spectrosc. 84 (1980) 405 - 423 PDF 5. 1315 - 1986 G. Guelachvili, J. Opt. Soc. Am. 73 (1983) 137 - 150 PDF 6. 500 - 7782 SISAM database: http: //mark 4 sun. jpl. nasa. gov/ 7. 8564 - 9332 A. -W. Liu, S. -M. Hu, C. Camy-Peyret, J. -Y. Mandin, O. Naumenko, and B. Voronin, J. Mol. Spectry. 237 (2006) 53 - 62 PDF 4206 - 6600 A. Jenouvrier, L. Daumont, L. Regalia-Jarlot, V. G. Tyuterev, M. Carleer, A. C. Vandaele, S. Mikhailenko, S. Fally, J. Quant. Spectrosc. Rad. Transfer 105 (2007) 326 - 355 PDF 9. 6170 - 6747 P. Macko, D. Romanini, S. N. Mikhailenko, O. V. Naumenko, S. Kassi, A. Jenouvrier, Vl. G. Tyuterev, and A. Campargue, J. Mol. Spectry. 227 (2004) 90 - 108 PDF 10. 9711 - 10883 C. Camy-Peyret, J. -M. Flaud, J. -Y. Mandin, A. Bykov, O. Naumenko, L. Sinitsa, and B. Voronin, J. Quant. Spectrosc. Rad. Transfer 61 (1999) 795 - 812 PDF 11. 11365 - 14377 M. Tanaka, O. Naumenko, J. W. Brault, and J. Tennyson, J. Mol. Spectrosc. 234 (2005) 1 - 9 PDF 8. Download

H 217 O vibrational energy levels n 1 n 2 n 3 MARVEL No. of levels 000 0. 000000 194 010 1591. 325708(48) 153 020 3144. 980414(31) 63 100 3653. 142263 (21) 106 001 3748. 318070(11) 143 030 [4657. 123] 22 110 5227. 705603 (46) 68 011 5320. 260507(3) 148 040 [6121. 552] 21 120 6764. 725603(547) 63 021 6857. 272709(32) 89 200 7193. 246623(20) 83 101 7238. 713600(185) 102 002 7431. 076115(1449) 28 050 1

MARVELlous water H 216 O H 218 O HD 16 O 8 463 25 367 50 674 42 17 20 30 ~37000 16 876 16 855 22 455 No. of HITRAN transitions 6 120 9 531 9 627 Concordant transitions 4 586 8 918 6 876 Absent HITRAN transitions 1 910 607 25 325 No. of transitions collected Maximum J Highest VBO (cm-1) ~250 000 H 217 O Characteristics of MARVEL energy levels: • highly accurate • highly incomplete as we move up on the energy ladder

Pure rotational energy levels for water T. Furtenbacher, A. G. Császár, J. Quant. Spectr. Rad. Transfer 109, 1234 (2008) H 216 O J Ka Kc H 217 O CVRQD FIS 3 MARVEL 1 0 1 23, 795 23, 794350 1 1 1 37, 138 37, 139 1 1 0 42, 372 2 0 2 CVRQD H 218 O FIS 3 MARVEL CVRQD FIS 3 MARVEL 23, 774 23, 773510 23, 756 23, 754902 37, 137125 36, 932 36, 933 36, 931110 36, 749 36, 750 36, 748650 42, 373 42, 371735 42, 188 42, 186934 42, 024 42, 023431 70, 094 70, 090815 70, 077 70, 008 70, 004668 69, 930 69, 927441 2 79, 499 79, 500 79, 496379 79, 230 79, 231 79, 227336 78, 991 78, 992 78, 988652 2 1 1 95, 178 95, 179 95, 175939 94, 973 94, 974 94, 970540 94, 791 94, 788651 2 2 1 134, 903 134, 906 134, 90163 134, 14526 133, 478 133, 480 133, 47580 2 2 0 136, 165 136, 168 136, 16392 135, 43118 134, 785 134, 788 134, 78312 3 0 3 136, 767 136, 768 136, 76165 136, 54 136, 53761 136, 342 136, 33666 3 142, 284 142, 285 142, 27848 141, 90240 141, 573 141, 574 141, 56806

Energies/frequencies • • Have well developed protocol H 217 O, H 218 O and HD 16 O (nearly) complete H 216 O underway: all available data input, much missing Labeling remains an issue

Intensities: • Required to better than 1% for remote sensing • Very few laboratory determinations this accurate • Problems with consistency between measurements • Issues with dynamic range of any measurements • New ab initio CVR dipole accurate to about 3% (hope to do better soon)

Intensities of pure rotational transitions Calculations using CVR dipole surface of Lodi et al JCP, 128, 0440204 (2008) Lodi & Tennyson, JQSRT, 109, 1219 (2008).

Lodi & Tennyson, JQSRT, 109, 1219 (2008).

Bending fundamental: 1250 – 1750 cm-1 CVR calc = Lodi & Tennyson, unpublished. DLR = Coudert, Wagner et al (JMS in press)

Intensities: Analysis of allowed and forbidden rotational transitions using: (Lodi & Tennyson, JQSRT, 109, 1219 (2008). ). • 555 allowed, 846 forbidden lines > 10(-28) molecule/cm at 296 K 50 of which not in HITRAN or JPL • Good general agreement with HITRAN for these • Significant systematic errors identified in JPL database • Subsequent analysis of bending fundamental region suggests problem with strong lines in HITRAN Use purely ab initio calculated intensities to solve these problems? (Resonances? !) “UCL linelists” • Multiple sources for single region • Back filled for missing transitions with theory Will be IUPAC convention, HITRAN too?

A Database of Water Transitions from Experiment and Theory Members: Jonathan Tennyson (chair), P. F. Bernath, A. Campargue, M. R. Carleer, A. G. Császár, R. R. Gamache, J. Hodges, A. Jenouvrier, O. Naumenko, O. L. Polyansky, L. S. Rothman, R. A. Toth, A. C. Vandaele, N. F. Zobov, L. Brown Also: L Daumont, AZ Fazliev, T Furtenbacher, IF Gourdon, SN Mikhailenko, SV Shirin, BA Voronin, S Voronina, A Al Derzi UCL intensity work: L Lodi, M Barber, RN Tolchenov