ABSORPTION CROSS-SECTIONS IN HITRAN2016: MAJOR DATABASE UPDATE FOR ATMOSPHERIC, INDUSTRIAL, AND CLIMATE APPLICATIONS ROMAN V KOCHANOV, IOULI E GORDON, LAURENCE S. ROTHMAN, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA; KEITH SHINE, Department of Chemistry, University of Reading, Reading, United Kingdom; STEVEN W. SHARPE, TIMOTHY J. JOHNSON, Chemical Physics and Analysis, Pacific Northwest National Laboratory, Richland, WA, USA; JEREMY J. HARRISON, Department of Physics and Astronomy, University of Leicester, Leicester, United Kingdom; PETER F. BERNATH, Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA, USA; TIMOTHY WALLINGTON, Research and Advanced Engineering, Ford Motor Company, Dearborn, MI, USA; MANFRED BIRK, GEORG WAGNER, Remote Sensing Technology Institute, DLR, Wessling, Germany; CHRISTIAN HILL, Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, United Kingdom; International Symposium on Molecular Spectroscopy 72nd Meeting - June 19-23, 2017 - Champaign-Urbana, Illinois

Introduction Line-by-line parameters can be absent or incomplete Large polyatomic molecules (many normal modes, dense spectra, hard to analyze) Can be used in radiative transfer models, RE calculations, climate change tracking… Important to provide cross-sections in HITRAN covering wide spectral ranges and at diverse thermodynamic conditions

HITRAN cross-section format (.xsc) ASCII text format: 100 bytes header and data Header contains basic cross-section parameters Negative part of the spectra is zeroed-out

Parameters for cross-section (T,p)-set

HITRAN2012 VS HITRAN2016 HITRAN2012 absorption cross-section part includes: 50 compounds Contains halocarbons, hydrofluorocarbons, Sulfur- and fluorine-containing species, oxygenated and nitrogenated hydrocarbons Atmospherically relevant temperature and pressure range (temperature 180-335K, pressure up to 760Torr) Spectra measured in the IR and UV (some data up to 58500 cm-1) FT-IR technique 0.005-2 cm-1 resolution spectra broadened by air, N2, He, and pure

HITRAN2012 VS HITRAN2016 HITRAN2016 update features: 275 new molecules (=>325 in total) 2780 cross-section (T,p)-sets in total Contains categorized compounds for remote sensing, environment monitoring, climate applications, industrial pollution tracking, instrument calibration… Atmospherically relevant temperature and pressure range (temperature 180-362K, pressure up to 760Torr) Update contains spectra containing features in near, middle and far infrared. Measurements: CRDS (Ethane, 200 kHz resolution, Reed et Hodges. JQSRT 2015) FTS (0.005-2 cm-1 resolution) Spectra broadened by air, N2, He, and pure

Molecule categorization

HITRANonline absorption cross-section search http://hitran.org

HITRANonline absorption cross-section search http://hitran.org VALUE TYPE CFC-12 Acronym CCl2F2 Formula 75-71-8 CAS Dichlorodifluoromethane Name InChI=1S/CCl2F2/c2-1(3,4)5 InChI PXBRQCKWGAHEHS-UHFFFAOYSA-N InChiKey

HITRANonline absorption cross-section search http://hitran.org

Bibliography in HTML Bibliography in LaTeX

HITRAN2016 update sources: Pacific Northwest National Laboratory (PNNL) ~230 molecules in total, 1260 cross-section sets Reactive compounds, industrial pollutants 15 out of 30 urban air TOCs / EPA, 2017 Diluted by N2, 760 Torr and 5/25/50C per molecule 0.112 cm-1 resolution, ~550-7500 cm-1 range, high S/N, composite spectra Sharpe et al. 2004 (original paper) Johnson et al 2010 (biomass burning detection) 43 updated molecules 12 new molecules: 4-Methylvaleric acid, 4-Penten-1-ol, DL-Limonene, D-Limonene, 2,3-Dimethylfuran, 2,5-Dimethylfuran, 3,3-Demethyl-2-pentanol, Limonene oxide, Methyl 2-methylbutyrate, Menthol, 1-Penten-3-ol, Methyl vinyl ether

Example: acetaldehyde (CH3CHO) Update for cross-sections for acetaldehyde. Comparison of three cross-cross sections from PNNL [1] (update) with corresponding data from HITRAN2012 [2] (calibrated with PNNL data). [1] Sharpe SW, Johnson TJ et al. Gas-phase databases for quantitative infrared spectroscopy. Appl Spectrosc 2004;58:1452–61 [2] Tereszchuk KA, Bernath PF. Infrared absorption cross-sections for acetaldehyde 37 (CH3CHO) in the 3μm region. J Quant Spectrosc Radiat Transf 2011;112:990–3.

HITRAN2016 update sources: Halocarbons and related compounds review Ø. Hodnebrog et al. Global warming potentials and radiative efficiencies of halocarbons and related compounds: A comprehensive review. Rev Geophys 2013;51:300–78 CFCs, HCFCs, HFCs, PFCs, and many other types of compounds + REs, GWPs/GTPs, lifetimes, etc. 0.01-1.0 cm-1 resolution strong features in 1000-1500 cm-1 range 120 molecules, 160 cross-section sets

Recently measured cross-sections J.J. Harrison et al. CCl4, HFC-23, HCFC-22, HFC-134a, CFC-12 142 high-resolution (~0.015 cm-1) air-broadened cross-section temperature and pressure sets, FTS intensities calibrated using data from NIST and PNNL G. Wagner and M. Birk. Bromine nitrate (JQSRT 2016) 0.014 cm-1 resolution, 66 cross-sections sets broadened by air, v2 and v3 bands, FTS Z. Reed, J. Hodges. Ethane (JQSRT 2015) CRDS air and self-broadened spectra (x6), 200 KHz spectral resolution 45 cross-section sets for 19 halocarbons (in total), published in 2015-2017 by Wallington et al, Godin et al., Le Bris et al., Rodriguez et al (see refs in the upcoming paper)

Evaluating cross-sections All parameters are present (T,p,res., broad.) Any similar data from another source? Yes Yes Pick “best” cross-section T,p-set for each wavenumber range. Interpolate if grid is not equidistant. Compare by a set of criteria. Not always possible!

Evaluating cross-sections example: CF4

Acknowledgements HITRAN group Data suppliers: Keith Shine, University of Reading, UK Steven Sharpe, Timothy Johnson, PNNL, USA Tim Wallington, Ford Motor Company, USA Jeremy Harrison, University of Leicester, UK Manfred Birk, Georg Wagner, DLR, Germany Joseph Hodges, Zachary Reed, NIST, USA Funding: NASA PATM, PDART, AURA

Thanks for your attention!