The IUPAC Critical Evaluation of theThe IUPAC Critical Evaluation of the

Ro-vibrational Spectra of Water Vapor:Ro-vibrational Spectra of Water Vapor:

Results for HResults for H221818O, HO, H22

1717O, and HDO, and HD1616OO

Jonathan TennysonUniversity College London

Attila G. Császár, Tibor FurtenbacherLoránd Eötvös University

Alexander Z. FazlievInstitute of Atmospheric Optics

Laurence S. Rothman, Iouli E. GordonHarvard-Smithsonian Center for Astrophysics

Ohio State University, June 2008

OutlineOutline

► IUPAC (International Union of Pure and Applied Chemistry)Water Vapor Task Group

- Goals

► Results

► Database and Access Issues

A Database of Water Transitions from A Database of Water Transitions from Experiment and TheoryExperiment 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. Polyansky, L.S. Rothman,R.A. Toth, A.C. Vandaele, N. Zobov

Objective:Develop a compilation of experimental and theoretical line

positions, energy levels, intensities, and line-shape parameters for water vapor and all of its major isotopologues

Establish a database structure that retains and enables access to all critically evaluated data

Spectroscopic Spectroscopic NNetworks of etworks of WWaterater

Water (except for HDO) has two main SNs:

(Ka + Kc + 3) is even (Ka + Kc + 3) is odd (para) (ortho)

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.

MARVEL MARVEL SStepsteps

123 MARVEL No. of rotational 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

130 3

031 10

210 34

111 8792.544310(925) 108

060 1

012 8982.869215(966) 55

041 13

220 12

121 10311.202510(926) 75

022 1

300 65

201 10598.475610(926) 102

102 10853.505315(966) 53

003 46

131 11792.827010(6018) 31

310 28

211 12132.992610(926) 87

112 25

013 12541.225510(926) 39

141 1

042 1

320 3

221 13631.499810(1019) 53

400 29

071 13808.273310(926) 2

301 13812.158110(926) 75

202 14

103 14296.279510(370) 37

340 13

241 6

HH221717O vibrational energy levelsO vibrational energy levels

IUPAC vs HITRANRo-vibrational levels

for H217O

Bending Fundamental: 1250 – 1750 cm-1

Interval (cm-1) References

1. 0 - 170 J. Steenbeckeliers, CRAS Paris B273 (1971) 471

2. 0 - 170 F.C. De Lucia, J. Mol. Spectrosc. 56 (1975) 138 - 145

3. 0 - 177F. Matsushima, H. Nagase, T. Nakauchi, H. Odashima, and K. Takagi,

J. Mol. Spectrosc. 193 (1999) 217 – 223

4. 177 - 600 J. Kauppinen and E. Kyro, J. Mol. Spectrosc. 84 (1980) 405 - 423

5. 1315 - 1986 G. Guelachvili, J. Opt. Soc. Am. 73 (1983) 137 - 150

6. 500 - 7782 SISAM database: http://mark4sun.jpl.nasa.gov/

7. 8564 - 9332A.-W. Liu, S.-M. Hu, C. Camy-Peyret, J.-Y. Mandin, O. Naumenko, and

B. Voronin, J. Mol. Spectrosc. 237 (2006) 53 – 62

8. 4206 - 6600A. Jenouvrier, L. Daumont, L. Regalia-Jarlot, V. G. Tyuterev, M. Carleer,

A. C. Vandaele, S. Mikhailenko, and S. Fally,J. Quant. Spectrosc. Rad. Transfer 105 (2007) 326 – 355

9. 6170 - 6747P. Macko, D. Romanini, S. N. Mikhailenko, O. V. Naumenko, S. Kassi,

A. Jenouvrier, Vl. G. Tyuterev, and A. Campargue,J. Mol. Spectrosc. 227 (2004) 90 – 108

10. 9711 - 10883C. 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

11 11365 - 14377M. Tanaka, O. Naumenko, J. W. Brault, and J. Tennyson, J. Mol. Spectrosc. 234

(2005) 1 - 9

12. 16570 - 17125O. Naumenko, M. Sneep, M. Tanaka, S.V. Shirin, W. Ubachs, and J. Tennyson, J. Mol.

Spectrosc. 237 (2006) 63-69

Observed Transitions of HObserved Transitions of H221717O O

Basic requirement► System has mainly valid data. Data are valid if they are experimentally verified. A user can easily check which data are experimental, which are calculated and which

are of indefinite status. Requirements for sorts of data► System has to have primary (data and knowledge)

► System has to have expert (data and knowledge) based on formal and informal constraints. These constraints have to be explicitly formulated.

Requirements for embedded applications► Applications have to provide collective work with data and knowledge

manipulation (upload primary data and download primary and expert data and metadata, check information on formal constrains (selection rules, process types, …), decompose expert data on primary data sources, compare data, construct composite information sources)

Technical requirements► Short time of information actualization► Access (in any time and from practically any place)► Additional services for information processing

Requirements forRequirements for Information System on Spectroscopy (W@DIS) Information System on Spectroscopy (W@DIS)

Alexander FazlievAlexander Fazliev

We use term primary information sourceprimary information source to define the data and metadata which are the result of solution (measurement) of one of the above mentioned spectroscopy problems, related to one molecule and published as a definite resource (in a journal or via the web).

The composite information sourcescomposite information sources (for instance, HITRAN) are the sets of the primary information sources. But it’s rather difficult to check this composition consistence. One of the goals of W@DIS is to make the process of decomposition of the composite information sources on primary information sources automatic.

Information SourceInformation Source

14

W@DIS Information System W@DIS Information System State of the ArtState of the Art

Upload and download of line profile parameters Generation of semantic metadata

Data sources search, tabular and graphical data comparison, root mean square deviation

Line profilesDatabaseKnowledgebaseInterfaces

Upload and download of transitionsGeneration of semantic metadata

Data sources search, tabular and graphical data comparison, root mean square deviation

TransitionsDatabaseKnowledgebaseInterfaces

Upload and download of energy levels Generation of semantic metadata

Data sources search, tabular and graphical data comparison, root mean square deviation

Energy levelsDatabase

KnowledgebaseInterfaces

Data manipulation (upload, storage, presentation, download)

Primary data sourcesReferences

Database

Interfaces

ProblemsEntitiesPart of IS

Line Profile Line Profile Root mean square deviations

► A full set of original experimental and calculation data on water

molecules has been gathered in W@DIS. Number of primary data sources ~ 580

► A knowledgebase of water molecule information sources has been created. One contains more than 40000 facts.

► Informational model of molecular spectroscopy has been developed on

the example of C2v and Cs symmetry molecules. In W@DIS one can

work with the following molecules: H2O, O3, SO2, H2S

► W@DIS has facilities for pairwise comparison of data sets and

calculations of root-mean-square deviations, sets upload and download,…

► IS W@DIS – http://wadis.saga.iao.ru

Summary of Database Delivery SystemSummary of Database Delivery System