Anna Huff, Rebecca Mackenzie, CJ Smith, Ken Leopold

Facile Formation of Acetic Sulfuric Anhydride in a Supersonic Jet Characterization by Microwave Spectroscopy and Computational Chemistry Anna Huff, Rebecca Mackenzie, CJ Smith, Ken Leopold Department of Chemistry, University of Minnesota June 19, 2017 Gas Phase Hydrolysis of SO3 Formation of atmospheric sulfuric acid ~ 20 kcal/mol Morokuma, K.; Muguruma, C. J. Am. Chem. Soc. 1994, 116, 10316-10317. (Adapted by Hazra, M.K; Sinha, A.) Kolb, C.E. et al. J. Am. Chem. Soc. 1994, 116, 10314-10315. 2 Formic-acid catalyzed hydrolysis of SO3 Hazra, M.K; Sinha, A. J. Am. Chem. Soc. 2011, 133, 17444-53. 3 Discovering Formic Sulfuric Anhydride

(FSA) Looking for complexes containing HCOOH, SO3, H2O SO3H2OHCOOH Electronic Energy (kcal/mol) -11 -13 HCOOHSO -15 3 0.2 kcal/mol H2SO4HCOOH -17 CCSD(T)/CBS//M06-2X/6-311++G(3df,3pd), with ZPE -19 Mackenzie, R.B.; Dewberry, C.T.; Leopold, K.R. Science. 2015, 349, 58-61.

4 Potential atmospheric impacts Cluster or droplet R R + HCOOH RCOOH R H2SO4 Incorporation of volatile organics into atmospheric aerosol Production of H2SO4 in the atmosphere Establish a series of carboxylic sulfuric anhydrides 5 Tandem cavity and chirped-pulse FTMW spectrometer

Cavity Narrowband, ~1 MHz increments 2-8 kHz resolution and high sensitivity Chirp Broadband, 3 GHz spectral windows >30 kHz resolution and lower sensitivity 6 Pulsed nozzle source with on-the-fly mixing Pulse Line 2.3 atm Ar SO3 Continuous Flowline 0.67 atm Ar RCOOH 7 Chirping for another carboxylic sulfuric anhydride

CF CF33COOH COOH + SO3 trifluoroacetic sulfuric anhydride? (TFASA) TFA Background TFA-H2O 6 GHz 18 GHz No chirp observation of TFASA (But TFASA later observed in cavity) 8 (Still) Chirping for another carboxylic sulfuric anhydride CH3COOH + SO3 acetic sulfuric anhydride? (ASA) 43 303202 32 54

322221 65 321220 6 GHz 18 GHz 7762 Obtained rough fit of A state for ASA by end of the day 7807 [MHz] 9 Spectroscopic constants for parent ASA Parent A [MHz] 3630.8996(11) B [MHz] 1359.30700(28) C [MHz] 1235.79407(18) E

J [kHz] 0.0980(19) JK [kHz] 0.694(11) iJ [kHz] 52.2(10) iK [kHz] -440(16) i- [kHz] 12.5(13) 7762 V3 [cm-1] 241.093(30) [deg] 3.04(47) [deg] 33.122(34) I [u2]a 3.183 N 56 [kHz] 0.8 (a) Fixed to the value derived from the M06-2X/6-311++G(3df,3pd) structure ^ = ^

+ ^ + ^ 303 202 322 221 321 220 A A E E A 7807 [MHz] 10 Comparison of fit to computational results M06-2X/6-311+ +g(3df,3pd) 3652 1367

1243 263 28.9 3.00 A [MHz] B [MHz] C [MHz] V3 [cm-1] [deg] [deg] 13 CH3COOSO2OH % Difference Prediction Experimental Experimental 3630.8996(11) 1359.30700(28) 1235.79407(18) 241.093(30)

33.12(3) 3.04(47) % Difference -0.58 -0.55 -0.54 -9.1 13 1.3 CH3COO34SO2OH CD3COOSO2OD % Difference Prediction Experimental % Difference Prediction Experimental A

3635.08 -0.58 3614.0543(17) 3651.26 -0.583630.186(52) 3431.07 -0.493414.345(22) B 1338.10 -0.55 1330.78967(36) 1359.60 -0.55 1352.09806(23)

1259.74 -0.50 1253.47425(22) C 1216.83 -0.54 1210.29056(27) 1236.52 -0.54 1229.80579(28) 1140.29 -0.49 1134.73145(23) 11

Spectroscopic constants for observed ASA isotopologues A [MHz] B [MHz] C [MHz] J [kHz] JK [kHz] iJ [kHz] iK [kHz] i- [kHz] V3 [cm-1] [deg] [deg] I [u2]a N [kHz] Parent 3630.8996(11) 1359.30700(28) 1235.79407(18) 0.0980(19) 0.694(11) 52.2(10) -440(16) 12.5(13)

241.093(30) 3.04(47) 33.122(34) 3.183 56 0.8 CH3COOSO2OH 3614.0543(17) 1330.78967(36) 1210.29056(27) 0.0869(26) 0.700(17) 56.2(14) -470(21) 14.2(15) 241.080(42) 2.52(69) 32.708(52) 3.183 57 1.0 13 CH3COO34SO2OH

3630.186(52) 1352.09806(23) 1229.80579(28) 0.0944(37) 0.767(51) 52.2b -440b 12.5b 241.150(17) 2.61(53) 33.207(25) 3.183 23 1.4 (a) Fixed to the value derived from the M06-2X/6-311++G(3df,3pd) structure (b) Parameter fixed at the value determined from the parent fit CD3COOSO2OD 3414.345(22) 1253.47425(22) 1134.73145(23) 0.0783(19) 0.575(16) 52.2b

-440b 12.5b 234.57(13) 3.04b 31.59(22) 6.362 55 3.7 12 Computational work on ASA formation: Role of the methyl group Cycloaddition 60 reorientation H3CCOOH-SO3 ASA 13 Pathways for ASA formation Methyl rotation TS

H3CCOOH-SO3 Cycloaddition TS 2nd order saddle point ASA CCSD(T)/CBS//M06-2X/6-311++G(3df,3pd) Near-zero barrier in both sequential and simultaneous formation pathways 14 Significance of ASA Characterization of ASA supports the assertion that a wide variety of carboxylic acids react with SO3 in the gas phase to form carboxylic sulfuric anhydrides. Experimentally characterized -H -CH3 R R

-CF3 Computational only Pinic acid Benzoic acid -cis-C=CH2, -trans-C=CH2 -CCH 15 Possible atmospheric relevance Subsequent hydrolysis could provide a route for atmospheric H2SO4 production and incorporation of organic matter into atmospheric aerosol RCOOH R RCOOSO2OH + H2O H2SO4 RCOOHH2SO4 RCOOSO2OHH2O

Formation of carboxylic sulfuric anhydrides represents new sulfur chemistry 16 Acknowledgements Dr. Ken Leopold Dr. Becca Mackenzie CJ Smith 17 18 Acetic acid internal rotation barriers 241 cm-1 168 cm-1 138 cm-1 B. van Eijck. J. Mol. Spec. 1981, 86, 465-479.

Ouyang, B; Howard, B.J. Phys. Chem. Chem. Phys. 2008, 11, 366-373. *39 cm-1 118 cm-1 19 ASA pathways with and without ZPE 20 Atmospheric concentrations of carboxylic acids Chebbi, A.; Carlier, P. Atmos. Env. 1996, 30, 4233-4249. 21 Methyl internal rotation ^ = ^ + ^ + ^ Rigid rotor

Centrifugal distortion Internal rotation/ Overall rotation coupling Rotational energy levels spaced differently in A vs E state 22 W. Gordy and R. Cook. Microwave molecular spectra, 3 Ed.; Wiley: New York, 1984. rd XIAM (Internal Axis Method) = 2 + 2 + ( 2 2 ) principal axis system = 4 2 2 4 1 = ( ) + 3 ( 1 cos ( )) 2 2 2 2

2 2 2 rho axis system 2 =22 ( ) P +Dpi2K [( ) + ( ) ]+ Dpi2 HID diagonalized in the RAS then rotated/transformed into the PAS Hartwig, H. and Dreizler, H. Z. Naturforsch. 1996, 51a, 923 23 Spectroscopic constants for observed ASA isotopologues 13 CH3COOSO2OH CH3COO34SO2OH CD3COOSO2OD Parent A [MHz] 3630.8996(11) 3614.0543(17) 3630.186(52) 3414.345(22)

B [MHz] 1359.30700(28) 1330.78967(36) 1352.09806(23) 1253.47425(22) C [MHz] 1235.79407(18) 1210.29056(27) 1229.80579(28) 1134.73145(23) J [kHz] b 0.0944(37) 0.0980(19) 0.0869(26) 0.0783(19) JK [kHz] 0.694(11) 0.700(17) 0.767(51) 0.575(16) iJ [kHz] 52.2(10) 56.2(14) 52.2b 52.2b c iK [kHz] -440(16) -470(21)

-440b -440b 12.5b i- [kHz] 12.5(13) 14.2(15) 12.5b V3 [cm-1] 241.093(30) 241.080(42) 241.150(17) 234.57(13) [deg] 3.04(47) 2.52(69) 2.61(53) 3.04b b 33.207(25) [deg] 33.122(34) 32.708(52) 31.59(22) I [u2]a 3.183 3.183 3.183

6.362 N 56 57 23 55 [kHz] 0.8 1.0 a 1.4 3.7 (a) Fixed to the value derived from the M06-2X/6-311++G(3df,3pd) structure (b) Parameter fixed at the value determined from the parent fit = + + 24 FSA computational work 25 E lectro n ic E n erg y w ith Z P E (k cal/m o l)

Formation of ASA TS TFA-SO3 0.63 kcal AA-SO3 -0.46 kcal 1.5 0.5 TS TFASA ASA 26

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