New analysis of the 3 & 4 bands of HNO 3 by high resolution Fourier transform spectroscopy in the 7.6 µm region Agnés Perrin,, J.M.Flaud Laboratoire Interuniversitaire des Systémes Atmosphériques (LISA), CNRS, Université Paris Est, Créteil M.Ridolfi, M.Carlotti, Dipartimento di Chimica Fisica e Inorganica (DCFI), Universiy of Bologna, Viale del Risorgimento, 4 40136, - Bologna, Italy. Agnes.Perrin@lisa.u-pec.fr A.Perrin: ASA-HITRAN 2012
HNO 3 in HITRAN-GEISA Intensities MW & 9 { 5,2 9 ) { 4, 3 } 2 0-10cm -1 458cm -1 879, 896cm -1 1303, 1326cm-1 1709cm -1 Far-IR 22µm 11µm 7.6µm 5.8µm Spectral range covered by ACE-FTS & MIPAS A.PerrinASA-HITRAN 2012
Intensities Up to now HNO 3 is measured (almost only) in the 11 µm region Which was updated recently in HITRAN MW & 9 { 5,2 9 ) { 4, 3 } 2 0-10cm -1 458cm -1 879, 896cm -1 1303, 1326cm-1 1709cm -1 Far-IR 22µm 11µm 7.6µm 5.8µm Improved line positions & intensities at 11 µm ( 5 and 2 9 bands): Coherence in the HNO 3 line intensities for the 11µm 7.6 µm 5.8 µm Perrin, Orphal, Flaud, Klee, Mellau, Mäder, Walbrodt & Winnewisser, i J. Mol. Spect 228 (2004) Flaud, Brizzi, Carlotti, A.Perrin: Perrin & Ridolfi Ohio-State Atmos. 67th Chem. Molecular Phys., Symposium, 6, 1 12, 2006. June 2012 Tran, Brizzi Gomez, Perrin, Hase, Ridolfi, Hartmann, JQSRT 110, 109-117 (2009). Gomez, Tran, Perrin, Gamache, Laraia, Orphal, Chelin, Fellows, Hartmann JQSRT 110, 675-686 (2009).
900 cm -1 11 µm 1300 cm -1 7.6 µm 1700 cm -1 5.6 µm ACE-FTS
900 cm -1 11 µm 1300 cm -1 7.6 µm 1700 cm -1 5.6 µm ACE-FTS Difference between the two profiles (900 cm -1 and 1700cm -1 bands) M. A. Wolff, Validation of HNO 3, ClONO 2, and N 2 O 5 from the the ACE-FTS spectrometer. Atmos. Chem. Phys., 8, 3529 3562, 2008
Only ONE source for the line positions & relative intensities parameters for HNO 3 @7.6 µm in the HITRAN or GEISA databases
Only ONE source for the line positions & relative intensities parameters for HNO 3 @7.6 µm in the HITRAN or GEISA databases Perrin, Lado-Bordowski d and dvalentin, «The 3 3 and 4 4 bands of HNO 3».Mol. Phys 67 p249 (1989) Perrin, et al. «Line intensities in the 11µm & 7.6 µm bands of HNO 3» J. Mol; Spectrosc. 160, p524 (1993)
Only ONE source for the line positions & relative intensities parameters for HNO 3 @7.6 µm in the HITRAN or GEISA databases Perrin, Lado-Bordowski d and dvalentin, «The 3 3 and 4 4 bands of HNO 3».Mol. Phys 67 p249 (1989) Perrin, et al. «Line intensities in the 11µm & 7.6 µm bands of HNO 3» J. Mol; Spectrosc. 160, p524 (1993) The HITRAN or GEISA updates of HNO3@7.6 µm concern only the total band intensity. Flaud, Bi Brizzi, i Carlotti, Perrin, and Ridolfi. MIPAS database: Validation of HNO 3 line parameters Atmos. Chem. Phys., 6, 1 12, 2006
Only ONE source for the line positions & relative intensities parameters for HNO 3 @76µmin @7.6 the HITRAN or GEISA databases Perrin, Lado-Bordowski d and dvalentin, «The 3 3 and 4 4 bands of HNO 3».Mol. Phys 67 p249 (1989) Perrin, et al. «Line intensities in the 11µm & 7.6 µm bands of HNO 3» J. Mol; Spectrosc. 160, p524 (1993) In 2011 Geoffrey Toon (JPL laboratory) evaluated the HNO 3 linelist in HITRAN @ 7.6 µm by using it to fit the JPL MkIV balloon spectra and PNNL laboratory spectra. PNNL spectra: Chackerian, Sharpe & Blake JQSRT, 82, 429-441, 2003.
Geoffrey Toon powerpoint presentation PNNL spectra MkIV balloon born spectra
7.6 µm( 3 & 4 bands) in 1989 Only a partial analysis of the 3 and 4 bands was performed 1303 cm-1 1326 cm-1 4 3 4 1 3 1 4 1 W Anh +C 3 1 Anh +C W The model did not account from the resonances involving the dark bands A.Perrin, O.Lado-Bordowski, & A. Valentin, Mol. Phys. 67, 249 (1989). Line position calculation: the calculated l energy levelsl were replaced A.Perrin: Ohio-State 67th Molecular Symposium, June 2012 by the observed ones (when existing)
This work FTS spectra recorded at Giessen (Germany) Bruker- 120HR in 2003 (7.6 µm) (1) FTS spectra recorded at Denver University (USA) for the 3 9-9 hot band 12 µm (2) FTS spectra recorded at Orsay for the 5+ 9-9 hot band 11 µm (3) Investigation of the PNNL HNO 3 cross sections (Pacific Northwest t National Laboratory)(4) Analyses of these spectra: New theoretical model (1)Perrin, Orphal,Flaud, Klee, Mellau,Mäder,Walbrodt,& Winnewisser, J. Mol. Spect 228 (2004) 375 391391 (2) Perrin, Flaud, Camy-Peyret, Winnewisser, Klee, Goldman, Murcray, Blatherwick, Bonomo, Murcray, J. Mol. Spectrosc. 166 (1994) 224 243 (3) Flaud, Perrin; Orphal, Kou, Flaud, Dutkiewicz, Piccolo, JQSRT 77 (2003) 355 364 A.Perrin: Ohio-State 67th Molecular Symposium, June 2012 (4) Chackerian; Sharpe, & Blake, JQSRT 82 (2003) 429 441
76 7.6 µm( 3 & 4 bands) in 2012 Two bright bands ( 3 & 4 ) four dark interacting bands.. (3 9, 2 6, 5 + 9 & 7 + 8 ) From the analysis of all investigated spectra: the 1 1 3 number of assigned energy levels {3 1,4 1, 9 3, 5 1 9 1, 6 2,7 1 8 1 } is multiplied by a factor of ~2 as compared to the 1989 study A.Perrin: ASA-HITRAN 2012
Hamiltonian matrix A.Perrin: ASA-HITRAN 2012
. 5 + 9 Informations on the: * 5 1 9 1 dark state from the Q branch of the 5 + 9-9 hot band A.Perrin: ASA-HITRAN 2012 5 9 9
Position of the 5 + 9 dark band (center at 1343.6 cm -1 ) from the 5 + 9-5 hot band Obs Orsay, 2003 (3) Flaud, Perrin; Orphal, Kou, Flaud, Dutkiewicz, Piccolo, JQSRT 77 (2003) 355 364
.3 9 Hamiltonian matrix E v = 1289.2 1293.2 1303.1 1326.2 1339.2 1342.9 (cm -1 ) sym: A' A" A' A' A" A" 6 2 9 3 4 1 3 1 5 1 9 1 7 1 8 1 6 2 W Fermi+C Fermi+C 9 3 W+Torsion B B strong Fermi 4 1 Fermi+C B W Anh 3 1 Fermi+C B Anh W A+B A+B 5 1 9 1 strong Fermi A+B A+B W A+B 7 1 8 1 A+B A+B W Informations on the: 9 3 dark state from the 3 9-9 hot band 9 9 Large amplitude OH torsion
O O N O H 9 torsion OH/NO 2 (3 9 at 1293.2cm -1 ) x O x H O H B N O N z y O y O z 9 torsion of OH /NO 2 large amplitude A.Perrin: Splitting Ohio-State of 62th ~ Molecular 0.06 cm Symposium, -1 in 9June 3 2007
Obs Denver 1994 A.Perrin: Ohio-State 67th Molecular Symposium, June 2012 (2) Perrin, Flaud, Camy-Peyret, Winnewisser, Klee, Goldman, Murcray, Blatherwick, Bonomo, Murcray, J. Mol. Spectrosc. 166 (1994) 224 243
Transfert of the torsional splitting via the 4 3 9 interaction Giessen 2003 A.Perrin: Ohio-State 67th Molecular Symposium, June 2012
Geoffrey Toon powerpoint presentation PNNL spectra MkIV balloon born spectra
Laboratory FTS spectrum (Univ. Giessen) Near 1320 cm -1 Spectre FTS de laboratoire (Univ. Giessen) A.Perrin ASA-HITRAN 2012
Laboratory FTS spectrum (Univ. Giessen) Near 1320 cm -1 Spectre FTS de laboratoire (Univ. Giessen) July 2012
Validation using MIPAS spectra A.Perrin: ASA-HITRAN 2012
HNO 3 detection by MIPAS at 1321 cm -1 MIPAS orbit 2081, July 2002, 0.025 cm -1 resolution Obs HITRAN-GEISA NEW Obs-Calc HITRAN-GEISA NEW A.Perrin, ASA-HITRAN 2012
Geoffrey Toon powerpoint presentation PNNL spectra MkIV balloon born spectra
A.Perrin: Ohio-State 67th Molecular Symposium, June 2012
A.Perrin: ASA-HITRAN 2012
MIPAS orbit 2081, July 2002, 0.025 cm -1 resolution Obs HITRAN NEW Obs-Calc HITRAN NEW A.Perrin: Ohio-State 67th Molecular Symposium, June 2012
Geoffrey Toon powerpoint presentation PNNL spectra MkIV balloon born spectra
Obs (Giessen, 2003)
+ 9-9. 3 + Calc. 3 4 bands 2012 Obs (Giessen, 2003)
MIPAS orbit 2081, July 2002, 0.025 cm -1 resolution Obs HITRAN. 3 + 9-9 NEW Obs-Calc HITRAN NEW A.Perrin: ASA-HITRAN 2012
What has still to be done: Try to get better fit for the line positions (if possible!!) Getting «absolute intensities» for all spectral ranges of the 3 & 4 bands at 7.6 µm Getting consistent t intensities iti for the 11 µm 7.6 µm 5.8 µm bands of HNO 3 I need high resolution data for HNO 3 for several infrared bands of HNO 3. ( band 3551 cm -1 1 @, 1 + 9 band @4006 cm -1, 2 2 band@2645cm -1, etc..please contact me! A.Perrin: Ohio-State 67th Molecular Symposium, June 2012
CONCLUSION A new study of the 3 et 4 bands of HNO 3 was performed It is necessary to account for resonances involving the 3 9, 2 6 et 5 + 9. & 7 + 8 dark bands. I need high resolution data for HNO 3. PLEASE CONTACT ME!!!!!!!!!!!! Financial support from the French program «LEFE- CHAT» (Les Enveloppes Fluides et l'environnement, Chimie Atmosphérique) of CNRS-INSU is gratefully A.Perrin: Ohio-State 67th Molecular Symposium, June 2012 acknowledged.