Formic Sulfuric Anhydride: A new chemical species with possible implications for atmospheric aerosol 1 Rebecca B. Mackenzie, Christopher T. Dewberry, and.

Slides:

Advertisements

Similar presentations

CHIRPED-PULSE FOURIER-TRANSFORM MICROWAVE SPECTROSCOPY OF THE PROTOTYPICAL C-H…π INTERACTION: THE BENZENE…ACETYLENE WEAKLY BOUND DIMER Nathan W. Ulrich,

Advertisements

MONITORING REACTION PRODUCTS USING CHIRPED-PULSE FOURIER TRANSFORM MICROWAVE SPECTROSCOPY Derek S. Frank, Daniel A. Obenchain, Wei Lin, Stewart E. Novick,

THE MICROWAVE SPECTRUM, STRUCTURE, AND DOUBLE PROTON EXCHANGE OF FORMIC ACID – NITRIC ACID Becca Mackenzie Chris Dewberry, Ken Leopold Department of Chemistry,

Galen Sedo, Jamie L. Doran, Shenghai Wu, Kenneth R. Leopold Department of Chemistry, University of Minnesota A Microwave Determination of the Barrier to.

Chirped-pulsed FTMW Spectrum of 4-Fluorobenzyl Alcohol

Chirped-Pulse Broadband Microwave Spectra and Structures of the OCS Trimer and Tetramer Luca Evangelisti, Cristobal Perez, Nathan A. Seifert, Brooks H.

Galen Sedo, Jane Curtis, Kenneth R. Leopold Department of Chemistry, University of Minnesota The Dipole Moment of the Sulfuric Acid Monomer.

Anion Photoelectron Spectroscopic Studies of NbC 4 H 4 ‾, NbC 6 H 6 ‾ and NbC 6 H 4 ‾ Products of Flow Tube Reactions of Niobium with Butadiene Melissa.

Galen Sedo Kenneth Leopold Group University of Minnesota A Microwave and ab initio Study of (CH 3 ) 3 CCN--SO 3.

Strategies for Complex Mixture Analysis in Broadband Microwave Spectroscopy Amanda L. Steber, Justin L. Neill, Matt T. Muckle, and Brooks H. Pate Department.

PURE ROTATIONAL SPECTRA OF THE REACTION PRODUCTS OF LASER ABLATED THORIUM METAL AND OXYGEN MOLECULES ENTRAINED WITHIN SUPERSONIC EXPANSIONS OF NOBLE GASES.

Microwave Spectroscopy and Proton Transfer Dynamics in the Formic Acid-Acetic Acid Dimer Brian Howard, Edward Steer, Michael Tayler, Bin Ouyang (Oxford.

Observation of the weakly bound (HCl) 2 H 2 O cluster by chirped-pulse FTMW spectroscopy Zbigniew Kisiel, a Alberto Lesarri, b Justin Neill, c Matt Muckle,

DANIEL P. ZALESKI, JUSTIN L. NEILL, MATTHEW T. MUCKLE, AMANDA L. STEBER, NATHAN A. SEIFERT, AND BROOKS H. PATE Department of Chemistry, University of Virginia,

Microwave Spectrum of Hydrogen Bonded Hexafluoroisopropanol  water Complex Abhishek Shahi Prof. E. Arunan Group Department of Inorganic and Physical.

FOURIER TRANSFORM MICROWAVE SPECTROSCOPY OF ALKALI METAL HYDROSULFIDES: DETECTION OF KSH P. M. SHERIDAN, M. K. L. BINNS, J. P. YOUNG Department of Chemistry.

Microwave Spectra and Structures of H 2 S-CuCl and H 2 O-CuCl Nicholas R. Walker, Felicity J. Roberts, Susanna L. Stephens, David Wheatley, Anthony C.

THE PURE ROTATIONAL SPECTRA OF THE TWO LOWEST ENERGY CONFORMERS OF n-BUTYL ETHYL ETHER. B. E. Long, G. S. Grubbs II, and S. A. Cooke RH13.

Daniel P. Zaleski, Hansjochen Köckert, Susanna L. Stephens, Nick R. Walker School of Chemistry, Bedson Building, Newcastle University, Newcastle upon Tyne,

Pulsed-jet discharge matrix isolation and computational study of Bromine atom complexes: Br---BrXCH 2 (X=H,Cl,Br) OSU 66 th International Symposium on.

Chirped-pulse, FTMW spectroscopy of the lactic acid-H 2 O system Zbigniew Kisiel, a Ewa Białkowska-Jaworska, a Daniel P. Zaleski, b Justin L. Neill, b.

Rotational Spectra and Structure of Phenylacetylene-Water Complex and Phenylacetylene-H 2 S (preliminary) Mausumi Goswami, L. Narasimhan, S. T. Manju and.

Steven T. Shipman, 1 Justin L. Neill, 2 Matt T. Muckle, 2 Richard D. Suenram, 2 and Brooks H. Pate 2 Chirped-Pulse Fourier Transform Microwave Spectroscopy.

Microwave Spectrum and Molecular Structure of the Argon-(E )-1-Chloro-1,2-Difluoroethylene Complex Mark D. Marshall, Helen O. Leung, Hannah Tandon, Joseph.

Galen Sedo, Jamie Doran, Jane Curtis, Kenneth R. Leopold Department of Chemistry, University of Minnesota A Microwave Study of the HNO 3 -(H 2 O) 3 Tetramer.

†) 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.

The Pure Rotational Spectrum of Pivaloyl Chloride, (CH 3 ) 3 CCOCl, between 800 and MHz. Garry S. Grubbs II, Christopher T. Dewberry, Kerry C. Etchison,

RANIL M. GURUSINGHE, MICHAEL TUBERGEN Department of Chemistry and Biochemistry, Kent State University, Kent, OH. RANIL M. GURUSINGHE, MICHAEL TUBERGEN.

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

Effective C 2v Symmetry in the Dimethyl Ether–Acetylene Dimer Sean A. Peebles, Josh J. Newby, Michal M. Serafin, and Rebecca A. Peebles Department of Chemistry,

Daniel P. Zaleski and Nick R. Walker School of Chemistry, Bedson Building, Newcastle University, Newcastle upon Tyne, NE1 7RU, UK. David P. Tew and Anthony.

June 18, rd International Symposium On Molecular Spectroscopy Gas-Phase Rotational Spectrum Of HZnCN (Χ 1 Σ + ) by Fourier Transform Microwave Techniques.

Perfluorobutyric acid and its monohydrate: a chirped pulse and cavity based Fourier transform microwave spectroscopic study Javix Thomas a, Agapito Serrato.

The Ohio State University International Symposium on Molecular Spectroscopy 68th Meeting - - June 17-21, 2013 Microwave Spectrum of Hexafluoroisopropanol,

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

Rotational Spectra Of Cyclopropylmethyl Germane And Cyclopropylmethyl Silane: Dipole Moment And Barrier To Methyl Group Rotation Rebecca A. Peebles, Sean.

Microwave Spectrum of the Ethanol-Water Dimer

0 ipc kiel The rotational spectrum of the pyrrole-ammonia complex Heinrich Mäder, Christian Rensing and Friedrich Temps Institut für Physikalische Chemie.

Intermolecular Interactions between Formaldehyde and Dimethyl Ether and between Formaldehyde and Dimethyl Sulfide in the Complex, Investigated by Fourier.

D. Zhao, K.D. Doney, H. Linnartz Sackler Laboratory for Astrophysics, Leiden Observatory, University of Leiden, the Netherlands T he 3 μm Infrared Spectra.

International Symposium on Molecular Spectroscopy// June 26, 2015

CHIRPED PULSE AND CAVITY FOURIER TRANSFORM MICROWAVE (CP-FTMW AND FTMW) SPECTRUM OF BROMOPERFLUOROACETONE NICHOLAS FORCE, DAVID JOSEPH GILLCRIST, CASSANDRA.

S TRUCTURE D ETERMINATION AND CH···F I NTERACTIONS IN H 2 C=CHF···H 2 C=CF 2 B Y F OURIER - T RANSFORM M ICROWAVE S PECTROSCOPY Rachel E. Dorris, Rebecca.

Broadband Microwave Spectroscopy to Study the Structure of Odorant Molecules and of Complexes in the Gas Phase Sabrina Zinn, Chris Medcraft, Thomas Betz,

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.

Helen O. Leung, Mark D. Marshall & Joseph P. Messenger Department of Chemistry Amherst College Supported by the National Science Foundation.

CHIRPED PULSE AND CAVITY FT MICROWAVE SPECTROSCOPY OF THE HCOOH – N(CH 3 ) 3 WEAKLY BOUND COMPLEX Rebecca B. Mackenzie, Christopher T. Dewberry, and Kenneth.

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 Spectra of N 2 O-H 2 Complexes University of Alberta Jen Nicole Landry and Wolfgang Jäger June 23, 2005.

THE PURE ROTATIONAL SPECTRUM OF PERFLUOROOCTANONITRILE, C 7 F 15 CN, STUDIED USING CAVITY- AND CHIRPED-PULSED FOURIER TRANSFORM MICROWAVE SPECTROSCOPIES.

FTIR and DFT Study of the Vibrational Spectrum of SiC 5 Trapped in Solid Ar T.H. Le, C.M.L. Rittby and W.R.M. Graham Department of Physics and Astronomy.

CRISTOBAL PEREZ, MARINA SEKUTOR, ANDREY A

Rotational spectra of C2D4-H2S, C2D4-D2S, C2D4-HDS and 13CH2CH2-H2S complexes: Molecular symmetry group analysis Mausumi Goswami and E. Arunan Inorganic.

A COMPARISON OF THE MOLECULAR STRUCTURES OF C4H9OCH3, C4H9SCH3, C5H11OCH3, AND C5H11SCH3 USING MICROWAVE SPECTROSCOPY BRITTANY E. LONG, Chemistry Department,

Pure rotational spectrum of the “non-polar” dimer of Formic acid

Facile Formation of Acetic Sulfuric Anhydride in a Supersonic Jet

Carlos Cabezas and Yasuki Endo

MICROWAVE FREQUENCY TRANSITIONS REQUIRING LASER ABLATED URANIUM METAL DISCOVERED USING CHIRP-PULSE FOURIER TRANSFORM MICROWAVE SPECTROSCOPY B. E. Long.

L. Evangelisti,a,c C. Perez,b,c B.H. Patec

G. S. Grubbs II*, S. A. Cooke⧧, and Stewart E. Novick*,

Becca Mackenzie Chris Dewberry, Ken Leopold

The Effect of Protic Acid Identity on the Structures of Complexes with Vinyl Chloride: Fourier Transform Microwave Spectroscopy and Molecular Structure.

CHIRPED-PULSE FOURIER TRANSFORM MICROWAVE SPECTROSCOPY OF

Microwave spectra of 1- and 2-bromobutane

Quantum Chemical Studies of Low-Energy Pathways to

ASSIGNMENT OF THE PERFLUOROPROPIONIC ACID-FORMIC ACID COMPLEX AND THE DIFFICULTIES OF INCLUDING HIGH Ka TRANSITIONS Daniel A. Obenchain, Eric A. Arsenault,

Wei Lin, Anan Wu, Zin Lu, Daniel A. Obenchain, Stewart E. Novick

Michal M. Serafin, Sean A. Peebles

1 MICROWAVE CHARACTERIZATION OF PROPIOLIC SULFURIC ANHYDRIDE AND TWO CONFORMERS OF ACRYLIC SULFURIC ANHYDRIDE C.J. Smith, Anna Huff, Becca Mackenzie, and.

THE MICROWAVE SPECTRUM AND UNEXPECTED STRUCTURE OF THE BIMOLECULAR COMPLEX FORMED BETWEEN ACETYLENE AND (Z)-1-CHLORO-2-FLUOROETHYLENE Nazir D. Khan, Helen.

Presentation transcript:

Formic Sulfuric Anhydride: A new chemical species with possible implications for atmospheric aerosol 1 Rebecca B. Mackenzie, Christopher T. Dewberry, and Kenneth R. Leopold Department of Chemistry, University of Minnesota 70 th International Symposium on Molecular Spectroscopy

2 Gases Complexes Solids & Liquids H 2 SO 4 + H 2 O + ??? Aerosols & Homogenous Nucleation Impact of aerosols

Gas Phase Formation of H 2 SO 4 Morokuma, K., Muguruma, C. J. Am. Chem. Soc. 116, 10316–10317 (1994). C.E. Kolb, J.T. Jayne, D.R. Worsnop, M.J. Molina, R.F Meads, A. Viggiano, J. Am. Chem. Soc. 116, (1994). Sulfuric acid is not directly emitted into the atmosphere SO 2, from both natural and anthropogenic sources, is converted to H 2 SO 4 through a series of steps Final step, the conversion from SO 3 and H 2 O to H 2 SO 4 3

Complexes Acting as Intermediates Hazra, M. K., Sinha, A. Journal of the American Chemical Society 2011, 133, 17444–

Frequency (MHz) UMN Fourier Transform Microwave Spectrometer (FTMW) 5 Cavity Experiment Chirp Experiment

Instrumental Setup SO 3 pulsed in with Ar HCOOH (88%) flowed in with Ar separately Used chirp and cavity jointly Chirps with Ar-SO 3 Ar-SO 3 -H 2 O Ar-SO 3 -H 2 O-HCOOH HCOOH & H 2 O in Ar SO 3 in Ar 6

Broadband Spectrum of Ar, SO 3, HCOOH, H 2 O Frequency (MHz)

Unknown Rotational Spectrum Fit Frequency (MHz) Unknown a-type spectrum SO 3 -H 2 O HCOOH Ar-SO 3

M06-2X/ G(3df,3pd) SO 3 ∙∙∙ HCOOHH 2 SO 4 ∙∙∙ HCOOH What Are We Observing? Observed Constant???? A (MHz) (12) B (MHz) (13) C (MHz) (13) Δ ID (amu Å 2 )-98.9 Δ J (kHz)0.3030(55) Δ JK (kHz)1.427(29) RMS (kHz)2 N23 Inertial defect indicative of structure 9

What Are We Observing? Observed M06-2X/ G(3df,3pd) Species????SO 3 ∙∙∙ HCOOH A (MHz) (12) B (MHz) (13) C (MHz) (13) Δ ID (amu Å 2 ) M06-2X/ G(3df,3pd) ???? Formic sulfuric anhydride

Confirmation of Formic Sulfuric Anhydride a-, b-, and c-type rotational transitions Isotopic substitutions – 13 C and 34 S seen in natural abundance – HCOOD & DCOOH HCOOD deuterium transfers – Isotopic shifts consistent with what DFT predicts a b c 11 µ a µ b µ c

Structure Analysis Kraitchman Equations Distance Experiment (Å ) DFT (Å ) Δ (Å)Δ (Å) C1-S (53) C1-H (99) C1-H92.615(10) S5-H (26) S5-H (23) COM 12 Formic Sulfuric Anhydride

Where does FSA fit in? (2) Hazra, M. K.; Sinha, A. Journal of the American Chemical Society 2011, 133, 17444– MP2/ G(3df,3pd) 13

14 Potential Energy Surface of HCOOH + H 2 O + SO 3 CCSD(T)/CBS(D-T)//MP2/ G(3df,3pd) FA + H 2 O + SO 3 H 2 O ∙∙∙ SO 3 FA ∙∙∙ H 2 O TS FSA FA ∙∙∙ SO 3

Proposed Mechanism π 2 + π 2 + σ 2 cycloaddition 15

ZPE Correction (MP2 frequencies) H 2 O ∙∙∙ SO 3 FA ∙∙∙ H 2 O TS FSA FA ∙∙∙ SO 3 16 Potential Energy Surface of HCOOH + H 2 O + SO 3 CCSD(T)/CBS(D-T)//MP2/ G(3df,3pd) FA + H 2 O + SO 3 H 2 O ∙∙∙ SO 3 FA ∙∙∙ H 2 O TS FSA FA ∙∙∙ SO 3

-0.5 kcal/mol M06-2X/ G(3df,3pd) ZPE corrected SO 3 ∙∙∙HOOCC 8 H 13 O 2 TS1 (PSA) Pinic sulfuric anhydride Extension of Mechanism 1.7 kcal/mol

18 Incorporation of Organics into Aerosols SO 3 + HCOOH → SO 3 ∙∙∙HCOOH SO 3 ∙∙∙HCOOH → FSA FSA + H 2 O (g or l) → H 2 SO 4(g or aq) + HCOOH (g or aq) (1) (2) (3) +H 2 SO 4 R R Evaporation R +H 2 SO 4 HOOCR Particle formation

Conclusions FSA forms readily from SO 3 + HCOOH – Computational work suggests a barrierless cycloaddition reaction – Requires the formation of only a dimer not a trimer Mechanism appears applicable to other carboxylic acids Hydrolysis could incorporate sulfuric acid and a carboxylic acid in prenucleation clusters 19

Funding & Acknowledgements Leopold Group Dr. Chris Dewberry Dr. Pete McMurry Dr. Tom Hoye Will Isley 20

21 Spectroscopic Constants ConstantHOSO 3 CHOHO 34 SO 3 CHOHOSO 3 13 CHODOSO 3 CHOHOSO 3 CDO A (MHz) (12) (28)4496.4(11) (21) (82) B (MHz) (13) (47) (13) (62) (27) C (MHz) (13) (47) (13) (67) (29) Δ ID (amuÅ 2 ) χ aa [D] (MHz) (56)0.0347(56) χ bb -χ cc [D] (MHz) (72) Δ J (kHz)0.3030(55)0.363(12)0.444(55)0.303(21)0.2940(98) Δ JK (kHz)1.427(29)--1.29(11)1.341(27) RMS (kHz)23362 N

Frequency (MHz) Unknown a-type spectrum Ar-SO 3 HCOOH SO 3 -H 2 O Unknown a-type Spectrum SO 3 -H 2 O HCOOH Ar-SO 3