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

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

1 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 2 Gases Complexes Solids & Liquids H 2 SO 4 + H 2 O + ??? Aerosols & Homogenous Nucleation Impact of aerosols

3 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, 10314-10315 (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

4 Complexes Acting as Intermediates Hazra, M. K., Sinha, A. Journal of the American Chemical Society 2011, 133, 17444–17453. 4

5 9000 12000 1000011000 Frequency (MHz) UMN Fourier Transform Microwave Spectrometer (FTMW) 5 Cavity Experiment Chirp Experiment 11768.0 11768.2

6 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

7 Broadband Spectrum of Ar, SO 3, HCOOH, H 2 O 7000900011000130001500017000 Frequency (MHz)

8 Unknown Rotational Spectrum Fit 8 7000900011000130001500017000 Frequency (MHz) Unknown a-type spectrum SO 3 -H 2 O HCOOH Ar-SO 3

9 M06-2X/6-311++G(3df,3pd) SO 3 ∙∙∙ HCOOHH 2 SO 4 ∙∙∙ HCOOH 4420.3163626.473 1802.5831020.113 1693.684945.728 -96.3-100.0 What Are We Observing? Observed Constant???? A (MHz)4510.1155(12) B (MHz)2013.28751(13) C (MHz)1913.33629(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

10 What Are We Observing? Observed M06-2X/ 6-311++G(3df,3pd) Species????SO 3 ∙∙∙ HCOOH A (MHz)4510.1155(12)4420.316 B (MHz)2013.28751(13)1802.583 C (MHz)1913.33629(13)1693.684 Δ ID (amu Å 2 )-98.9-96.3 M06-2X/ 6-311++G(3df,3pd) ???? 4541.675 2026.871 1926.747 -98.3 10 Formic sulfuric anhydride

11 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 - 3.188 µ b - 0.477 µ c - 0.973

12 Structure Analysis Kraitchman Equations 5 6 7 8 3 1 4 9 2 Distance Experiment (Å ) DFT (Å ) Δ (Å)Δ (Å) C1-S52.5938(53)2.58870.005 C1-H21.1054(99)1.09200.014 C1-H92.615(10)2.6340.019 S5-H92.0253(26)2.08450.059 S5-H23.5133(23)3.51360.000 COM 12 Formic Sulfuric Anhydride

13 Where does FSA fit in? (2) Hazra, M. K.; Sinha, A. Journal of the American Chemical Society 2011, 133, 17444–17453. MP2/6-311++G(3df,3pd) 13

14 14 Potential Energy Surface of HCOOH + H 2 O + SO 3 CCSD(T)/CBS(D-T)//MP2/6-311++G(3df,3pd) FA + H 2 O + SO 3 H 2 O ∙∙∙ SO 3 FA ∙∙∙ H 2 O TS FSA FA ∙∙∙ SO 3

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

16 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)//MP2/6-311++G(3df,3pd) FA + H 2 O + SO 3 H 2 O ∙∙∙ SO 3 FA ∙∙∙ H 2 O TS FSA FA ∙∙∙ SO 3

17 -0.5 kcal/mol M06-2X/6-311++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 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

19 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

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

21 21 Spectroscopic Constants ConstantHOSO 3 CHOHO 34 SO 3 CHOHOSO 3 13 CHODOSO 3 CHOHOSO 3 CDO A (MHz)4510.1155(12)4511.41(28)4496.4(11)4402.3855(21)4424.72510(82) B (MHz)2013.28751(13)2005.30074(47)1987.8089(13)2008.63262(62)1965.28477(27) C (MHz)1913.33629(13)1906.19874(47)1887.5407(13)1894.94290(67)1855.14994(29) Δ ID (amuÅ 2 )-98.9 -99.7-99.0 χ aa [D] (MHz)---0.1243(56)0.0347(56) χ bb -χ cc [D] (MHz)----0.1924(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 N23964727

22 7000900011000130001500017000 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

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