A b Submillimeter measurements of the Criegee intermediate CH 2 OO, in the gas phase ADAM M. DALY, BRIAN J. DROUIN, SHANSHAN YU Jet Propulsion Laboratory,

Slides:

Advertisements

Similar presentations

+ TERAHERTZ SPECROSCOPY OF METHYLAMINE R. A. Motiyenko, L. Margulès Laboratoire PhLAM, Université Lille 1, France V.V. Ilyushin, E.A. Alekseev Insitute.

Advertisements

Production of Molecular Ions Using a Hollow-Cathode Spectrometer Trevor Cross, Nadine Wehres, Mary Radhuber, Anne Carroll, Susanna Widicus Weaver Department.

Submillimeter-wave and far-infrared spectroscopy of high-J transitions of ammonia S. Yu, J.C. Pearson, B.J. Drouin and K. Sung Jet Propulsion Laboratory,

Toward a global model of low-lying vibrational states of methyl cyanide, CH 3 CN: the v 4 = 1 state at 920 cm –1 and its interactions with nearby states.

SUBMILLIMETER-WAVE ROTATIONAL SPECTRA OF DNC T. Amano Department of Chemistry and Department of Physics and Astronomy The University of Waterloo.

June 23rdJPL Spectral Line Catalog Brian J. Drouin, Herbert M. Pickett.

Remote Sensing Technology Institute 1 Cambridge, INFRARED ABSORPTION CROSS SECTIONS OF ClOOCl - LABORATORY WORK AND APPLICATION IN MIPAS-B.

Molecular Spectroscopy Symposium June 2008 HIGH RESOLUTION MOLECULAR SPECTROSCOPY FOR PLANETARY EXPLORATION John C. Pearson, Brian J. Drouin,

Molecular Spectroscopy Symposium June 2011 ROTATIONAL SPECTROSCOPY OF HD 18 O John C. Pearson, Shanshan Yu, Harshal Gupta, and Brian J. Drouin,

ESF-sponsored Workshop, Cagliari, Sardinia, Italia, October Active protection of passive radio services: towards a concerted strategy Frequency.

Terahertz spectroscopy of excited water Shanshan Yu, John Pearson, Brian Drouin Jet Propulsion Laboratory, California Institute of Technology, USA Adam.

Laboratory of Molecular Spectroscopy & Nano Materials, Pusan National University, Republic of Korea Spectroscopic Identification of New Aromatic Molecular.

Oxygen Atom Recombination in the Presence of Singlet Molecular Oxygen Michael Heaven Department of Chemistry Emory University, USA Valeriy Azyazov P.N.

High Resolution Measurements and Electronic Structure Calculations of a Diazanaphthalene: [1,6]-naphthyridine. Sébastien Gruet, Manuel Goubet, Olivier.

Molecular Spectroscopy Symposium June 2009 The Submillimeter Spectrum of the Ground Torsional State of CH 2 DOH J.C. PEARSON, C.S. BRAUER, S.

June 18, nd Symp. on Molec. Spectrosc. The Pure Rotational Spectra of VN (X 3  r ) and VO (X 4  - ): A Study of the Hyperfine Interactions Michael.

Chem. 31 – 4/1 Lecture.

Millimeter- Wave Spectroscopy of Hydrazoic acid (HN 3 ) Brent K. Amberger, Brian J. Esselman, R. Claude Woods, Robert J. McMahon University of Wisconsin.

Upper Stratospheric and Lower Mesospheric HO x :Theory and Observations Tim Canty 1, Herb Pickett 2, Brian Drouin 2, Ken Jucks 3, Ross Salawith 2 HO x.

Molecular Spectroscopy Symposium June 2011 TERAHERTZ SPECTROSCOPY OF HIGH K METHANOL TRANSITIONS John C. Pearson, Shanshan Yu, Harshal Gupta,

Marlon Ramos and Brian J. Drouin 6/23/ THz Spectrum of Methyl Bromide (CH 3 Br)

†) Currently at Department of Chemistry, University of Manitoba A Microwave Study of the HNO 3 -N(CH 3 ) 3 Complex Galen Sedo, † Kenneth R. Leopold Department.

Laboratory of Molecular Spectroscopy, Pusan National University, Pusan, Republic of Korea Spectroscopic identification of isomeric trimethylbenzyl radicals.

The Simplest Criegee Intermediate: (CH2OO): Equilibrium Structure and Possible Formation from Atmospheric Lightning Michael McCarthy, Kyle Crabtree, Oscar.

1 TORSION-ROTATION-VIBRATION EFFECTS IN THE v 20, 2 v 21, 2 v 13 AND v 21 + v 13 STATES OF CH 3 CH 2 CN Adam M. Daly, John C. Pearson, Shanshan Yu, Brian.

Molecular Spectroscopy Symposium June 2013 Modeling the Spectrum of the 2 2 and 4 States of Ammonia to Experimental Accuracy John C. Pearson.

June 16-20, rd International Symposium on Molecular Spectroscopy Direct Measurements of the Fundamental Rotational Transitions of CD and 13 CH.

Fourier transform microwave spectra of CO–dimethyl sulfide and CO–ethylene sulfide Akinori Sato, Yoshiyuki Kawashima and Eizi Hirota * The Graduate University.

A LABORATORY AND THEORETICAL INVESTIGATION OF THE SILICON SULFUR MOLECULES H 2 SiS AND Si 2 S. MICHAEL C. MCCARTHY 1, PATRICK THADDEUS 1, HARSHAL GUPTA.

TA05 THE ROTATIONAL SPECTRA OF O-17 SUBSTITUTED OXYGEN SINGLET DELTA BRIAN J. DROUIN, HARSHAL GUPTA, SHANSHAN YU, CHARLES E. MILLER, Jet Propulsion Laboratory,

BRIAN J. DROUIN, VIVIENNE PAYNE, FABIANO OYAFUSO, KEEYOON SUNG, Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Dr., Pasadena,

The Pure Rotational Spectrum of TiCl + (X 3  r ) by Velocity Modulation Spectroscopy DeWayne T. Halfen and Lucy M. Ziurys Department of Chemistry Department.

1 The rotational spectrum of 13 CH 3 NH 2 up to 1 THz Roman A. Motiyenko, Laurent Margulès PhLAM, Université Lille 1 Vadim Ilyushin Institute of Radio.

National Aeronautics and Space Administration Aura Validation Large Balloons: Recent Campaigns and Table Mountain NO 2 Intercomparison Jim Margitan and.

Study of the CH 2 I + O 2 Reaction with a Step-scan Fourier-transform Infrared Absorption Spectrometer: Spectra of the Criegee Intermediate CH 2 OO and.

Molecular Spectroscopy Symposium June 2013 Identification and Assignment of the First Excited Torsional State of CH 2 DOH Within the o 2, e.

Copyright All rights reserved. June 25, 2015ISMS, 2015

The Millimeter- and Submillimeter-Wave Spectrum of Propenal A. M. DALY, C. BERMÚDEZ, L. KOLESNIKOVÁ, AND J. L. ALONSO Grupo de Espectroscopia Molecular.

Copyright All rights reserved.. Introduction to the hydronium ion (H 3 O + )  H 3 O + has a pyramidal structure and is iso-electronic to ammonia.

A Joint Theoretical and Experimental Study of the SiO 2 H 2 Isomeric System Michael C. McCarthy Harvard-Smithsonian Center for Astrophysics Jürgen Gauss.

Near-Infrared Photochemistry of Atmospheric Nitrites Paul Wennberg, Coleen Roehl, Geoff Blake, and Sergey Nizkorodov California Institute of Technology.

The rotational spectrum of acrylonitrile to 1.67 THz Zbigniew Kisiel, Lech Pszczółkowski Institute of Physics, Polish Academy of Sciences Brian J. Drouin,

International Symposium on Molecular Spectroscopy// June 26, 2015

1. 2 Natural Anthropogenic 3  Production of OH radical  An important source of HOx  The observed yields: 10% - 100%.  Generate Criegee intermediate.

Update of the analysis of the pure rotational spectrum of excited vibrational states of CH 3 CH 2 CN Adam Daly, John Pearson, Shanshan Yu, Brian Drouin.

THE J = 1 – 0 ROTATIONAL TRANSITIONS OF 12 CH +, 13 CH +, AND CD + T. Amano Department of Chemistry and Department of Physics and Astronomy The University.

Absolute VUV photoionization spectra for HCHO, HO 2, and H 2 O 2 from eV Leah G. Dodson, 1 Linhan Shen, 1 John D. Savee, 2 Nathan C. Eddingsaas,

Laser spectroscopy of a halocarbocation: CH 2 I + Chong Tao, Calvin Mukarakate, and Scott A. Reid Department of Chemistry, Marquette University 61 st International.

June 18, nd Symp. on Molec. Spectrosc. Activation of C-H Bonds: Pure Rotational Spectroscopy of HZnCH 3 ( 1 A 1 ) M. A. Flory A. J. Apponi and.

THz Spectroscopy of 1d-ethane: Assignment of v 18 ADAM M. DALY, BRIAN J. DROUIN, LINDA BROWN Jet Propulsion Laboratory, California Institute of Technology,

June 19, 2012 (Toho Univ. a, Univ. Toyama b ) ○Yuta Motoki a, Yukari Tsunoda a, Hiroyuki Ozeki a, Kaori Kobayashi b Hiroyuki Ozeki a, Kaori Kobayashi b.

(Toho Univ. a, Univ. Toyama b ) Chiho Fujita a, Hiroyuki Ozeki a, and Kaori Kobayashi b 2015 Jun 22ndInternational Symposium on Molecular Spectroscopy,

Terahertz spectroscopy of deuterated methylene bi-radicals, CHD and CD 2 Stéphane Bailleux June 25, 2015 – 70 th ISMS.

SESAPS Terahertz Rotational Spectrum of the v5/2v9 Dyad of Nitric Acid * Paul Helminger, a Douglas T. Petkie, b Ivan Medvedev, b and Frank C. De.

The Rotational Spectrum of the Water–Hydroperoxy Radical (H 2 O–HO 2 ) Complex Kohsuke Suma, Yoshihiro Sumiyoshi, and Yasuki Endo Department of Basic Science,

Rotational transitions in the and vibrational states of cis-HCOOH 7 9 Oleg I. Baskakov Department of Quantum Radiophysics, Kharkov National University.

Initial Development of High Precision, High Resolution Ion Beam Spectrometer in the Near- Infrared Michael Porambo, Brian Siller, Andrew Mills, Manori.

Kinetics measurements of HO 2 and RO 2 self and cross reactions using infrared kinetic spectroscopy (IRKS) A.C. Noell, L. S. Alconcel, D.J. Robichaud,

Microwave Spectroscopy of the Excited Vibrational States of Methanol John Pearson, Adam Daly, Jet Propulsion Laboratory, California Institute of Technology,

Carlos Cabezas and Yasuki Endo

V. Ilyushin1, I. Armieieva1, O. Zakharenko2, H. S. P. Müller2, F

Shanshan Yu, Brian J. Drouin, John C. Pearson, and Takayoshi Amano

Acetaldehyde: Into the Submillimeter

Vibrational energies for acrylonitrile from

The Pure Rotational Spectrum of FeO+ (X6S+)

IR Spectra of CH2OO at resolution 0

Terahertz spectroscopy of the ground state of methylamine (CH3NH2)

A. M. Daly, B. J. Drouin, J. C. Pearson, K. Sung, L. R. Brown

Fourier Transform Infrared Spectral

Determination of uptake coefficients ClO radicals with surfaces of sea

Presentation transcript:

a b Submillimeter measurements of the Criegee intermediate CH 2 OO, in the gas phase ADAM M. DALY, BRIAN J. DROUIN, SHANSHAN YU Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Dr., Pasadena, CA June 18, 2014 WH07 1 Journal of Molecular Spectroscopy, Volume 297, March 2014, Pages 16-20, ISSN ,

a b Environmental Aspects OH radical reservoir NOx and OHx budget Atmospheric Aspects Lightning of methane Ethylene reactions with ozone M. C. McCarthy, L. Cheng, K. N. Crabtree, O. Martinez, T. L. Nguyen, C. C. Womack, J. F. Stanton, J. Phys. Chem. Lett., (2013) Ultimately we would like to study C 2 H 4 with O 3  CH 2 OO June 18, 2014WH072

a b The first direct detection of CH 2 OO: First with Cl-initiated oxidation of DMSO using photoionization and mass spectroscopy made by Taatjes et al. J.A.C.S (2008),130, Followed by photolysis of CH 2 I 2 in excess O 2 in Welz, et al. Science 335, (2012) 204. Now there are numerous studies: Microwave: CH 2 Br 2 + O 2 and CH 2 OO – Microwave Nakajima and Endo, J. Chem. Phys. 139, (2013) CH 4 + O 2 to make CH 2 OO – Microwave McCarthy, et al. J. Phys. Chem Lett. 4, (2013), 4133 Infrared: CH 2 I 2 + O 2 to make CH 2 OO Su, et al. Science 340, (2013) 174 UV CH 2 I 2 + O 2 to make CH 2 OO Beames, et al. J.A.C.S. (2012), 134, What about the submillimeter? Only 4 transitions had been measured in both microwave studies! Kisiel, et al. J. Chem. Phys 105 (1996) 1778 June 18, 2014WH073

a b a b Simplest Criegee Intermediate : Ozonolysis of ethylene R. Criegee, Angew. Chem. Int. Ed. Engl., 14 (1975) 745–752 and CH 2 OO(?) NASA atmosphere investigations: HOONO, IO, OH, HO 2, BrO, O 3, CH 3 Cl, ClO, CO, H 2 O HCl, HCN, HOCl, N 2 O, SO 2. June 18, 2014WH074

a b JPL/SAO balloon payload just prior to launch 9/22/07 Combined payload includes: Submillimeter Limb Sounder PI - Robert Stachnik Mark IV solar interferometer PI – Geoffrey Toon Balloon OH limb sounder PI – Herbert Pickett Far-Infrared Spectrometer PI – Kenneth Jucks (SAO/HQ) FIR remote emission measurements have focused on radicals e.g. OH, HO 2, BrO, ClO. (low concentration species) Stachnik RA, Millan L, Jarnot R, Monroe R, McLinden C, Kuehl S, Pukite J, Shiotani M, Suzuki M, Kasai Y. Stratospheric BrO abundance measured by a balloon-borne submillimeterwave radiometer. Atmospheric Chemistry and Physics 2013 Mar 22;13(6): This measurement of the THz spectrum of the Criegee intermediate allows remote sensing instruments like SLS and FIRS-2 to ‘see’ it in the earth’s atmosphere June 18, 2014WH075

a b λ(μm) 1.00× × ×10 -3 ( )× × ×10 6 Cosmic Rays γ-Rays X-Rays UV Visible Infrared Microwave Radio  (Hz) 3.00× × ×10 16 ( )× × ×10 8  (cm -1 ) 1.00× × ×10 6 ( )× × ×10 -2 The electromagnetic spectrum Terahertz Microwave and millimeter/submillimeter spectroscopy - Spectrum of isotopes and vibrational states are unique - In pulsed free jet: different confirmations and ground vibrational state - In static and flow cells: Multiple vibrational states up to 1000 cm -1 June 18, 2014WH076

a b CH 2 I 2 in the millimeter range CH 3 I HO 2 CH 2 IO IO CH 2 OO CH 2 I 2 with O 2  June 18, 2014WH077

a b a b MethodCCSDM06HF B3LYP M06HF triplet Basis set C,H,Oaug-cc-pVTZaug-cc-pV5Zaug-cc-pVTZ G** Expt* A (16) B (13) C (16) aa bb Table 1. Results of calculations performed with different methods and basis set for CH 2 OO. *Both a and b dipole detected through using double resonance June 18, 2014WH078 9 sets of rotational constants from Isotopic substitution: 13 C, 18 O and 2 H reported in the two Microwave papers.

a b a b MethodCCSDM06HF B3LYP M06HF triplet Basis set C,H,Oaug-cc-pVTZaug-cc-pV5Zaug-cc-pVTZ G** Expt* A (16) B (13) C (16) aa bb Table 1. Results of calculations performed with different methods and basis set for CH 2 OO. *Both a and b dipole detected through using double resonance June 18, 2014WH079

a b a b Experimental Optimum Settings: 40 mtorr Ar, 20 mtorr O2, with a current of 0.5 mA when 1 kV Frequency Range , and GHz June 18, 2014WH0710

a b a b Experimental Optimum Settings: 40 mtorr Ar, 20 mtorr O2, with a current of 0.5 mA when 1 kV Frequency Range , and GHz June 18, 2014WH0711

a b June 18, 2014WH0712 PA SN609WR-10 Amplifier Module APH347 PA SN725WR-10 Amplifier Module APH416 PA SN709WR-10 Amplifier Module APH414 Attenuator2dB fixed waveguide attenuator JPL PN SN5M1: 250 GHz Frequency Tripler

a b a b Experimental Optimum Settings: 40 mtorr Ar, 20 mtorr O2, with a current of 0.5 mA when 1 kV Frequency Range , and GHz June 18, 2014WH0713

a b CH 2 OO Formic Acid June 18, 2014WH0714

a b CH 2 OO Formic Acid June 18, 2014WH0715

a b June 18, 2014WH0716

a b June 18, 2014WH0717

a b June 18, 2014WH0718

a b June 18, 2014WH0719

a b a b Analysis This work s-reduction This work a-reductionMcCarthy et al.*Nakajima et al.** A/MHz (183) A /MHz (186) (122) (16) B/MHz (152) B /MHz (175) (127) (13) C/MHz (139) C /MHz (161) (131) (16) D J /kHz (810)  J /kHz (157) D JK /kHz (165)  JK /kHz (190) D K /kHz (119)  K /kHz (120) d 1 /kHz (878)  J /kHz (927) d 2 /kHz (787)  K /kHz (236) H J /mHz 8.200(232)  J /mHz (556)-- H JK /mHz (387)  JK /mHz 252.(127)-- H KJ /mHz (878)  KJ /mHz (452)-- h 1 /mHz 5.208(267)  J /mHz 5.577(291)-- h 2 /mHz 1.474(233)  JK /mHz -11.0(718)-- h 3 /mHz 0.526(108)  K /mHz (6725)-- N dist /N total 164/  fit / MHz Spectroscopic Parameters for CH 2 OO June 18, 2014WH0720

a b Detected formic acid and formaldehyde CH 3 I and IO Several unidentified species in the discharge of CH 2 I 2 and O 2 No b-type transitions could be observed up to 1.5 THz Initial studies with C 2 H 4 and O 3 in a flow system could not produced CH 2 OO June 18, 2014WH0721

a b a b Subsequent Work CH 4 and O 2 / C 2 H 4 and O 3 – Initial studies with ethylene and ozone were unsuccessful with and without discharge. CH 3 CHCOO – using CH 3 CHBr 2 + O 2 in the Microwave Nakajima and Endo – Using CH 3 CHI 2 + O 2 in the UV by Beams, et al. – CH 3 CH 2 OO observed by Rupper, et al using 3-pentanone and CH 3 CH 2 Br We have tried in the laboratory flow discharge with Ar/O 2 – CH 3 CH 2 OH, CH 3 CH 2 CN and CH 3 CH 2 I a a Extended ground fit and a tentative assignment of excited vibration state June 18, 2014WH0722

a b a b Acknowledgements Dr. Brian Drouin and Dr. Shanshan Yu The Sander group at JPL – Linhan Shen Tim Crawford NASA California Institute of Technology June 18, 2014WH0723