Transcript TE07-Rothman.ppt.ppt

The IUPAC Critical Evaluation of the
Ro-vibrational Spectra of Water Vapor:
Results for H218O, H217O, and HD16O
Jonathan Tennyson
University College London
Attila G. Császár, Tibor Furtenbacher
Loránd Eötvös University
Alexander Z. Fazliev
Institute of Atmospheric Optics
Laurence S. Rothman, Iouli E. Gordon
Harvard-Smithsonian Center for
Astrophysics
Ohio State University, June 2008
Outline
► IUPAC (International Union of Pure and Applied Chemistry)
Water Vapor Task Group
- Goals
► Results
► Database
and Access Issues
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. 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 Networks of Water
Water (except for HDO) has two main SNs:
(Ka + Kc + 3) is even
(para)
(Ka + Kc + 3) is odd
(ortho)
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.
H217O vibrational energy levels
123
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
IUPAC vs HITRAN
Ro-vibrational levels
for H217O
Bending Fundamental: 1250 – 1750 cm-1
Observed Transitions of H217O
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 - 177
F. 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 - 9332
A.-W. Liu, S.-M. Hu, C. Camy-Peyret, J.-Y. Mandin, O. Naumenko, and
B. Voronin, J. Mol. Spectrosc. 237 (2006) 53 – 62
4206 - 6600
A. 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 - 6747
P. 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 - 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
11
11365 - 14377
M. Tanaka, O. Naumenko, J. W. Brault, and J. Tennyson, J. Mol. Spectrosc. 234 (2005)
1-9
8.
Requirements for
Information System on Spectroscopy (W@DIS)
Alexander Fazliev
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
Information Source
We use term primary 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 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.
W@DIS Information System
State of the Art
Part of IS
Entities
Problems
Database
Data manipulation (upload, storage, presentation,
download)
Interfaces
Primary data
sources
References
Database
Energy levels
Upload and download of energy levels
Generation of semantic metadata
Data sources search, tabular and graphical data
comparison, root mean square deviation
Database
Knowledgebase
Interfaces
Transitions
Upload and download of transitions
Generation of semantic metadata
Data sources search, tabular and graphical data
comparison, root mean square deviation
Database
Knowledgebase
Interfaces
Line profiles
Upload and download of line profile parameters
Generation of semantic metadata
Data sources search, tabular and graphical data
comparison, root mean square deviation
Knowledgebase
Interfaces
14
Line Profile
Root mean square deviations
Summary of Database Delivery System
► 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