Yoon Jeong Choi, Alex Treviño, Susanna L. Stephens, Stephen A

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The rotational spectra of 4,4,4-trifluorobutyric acid and its complex with Formic acid Yoon Jeong Choi, Alex Treviño, Susanna L. Stephens, Stephen A. Cooke, Stewart E. Novick, Wei Lin WD04 Clusters and Complexes Wednesday 21th June 2017 09:21 – 09:36 AM

Chirp Pulse Experiment Center Frequency, ν, between 8-18 GHz Linear Frequency Sweep 0 – x - “Chirp” ν +/- x is amplified, pulsed and broadcast Excitation interacts with the molecules Free Induction Decay Collected, Amplified and Digitized on a 40 GS/s oscilloscope Chirp Pulse Experiment G.S. Grubbs, C.T. Dewberry, K.C. Etchison, K.E. Kerr, S.A. Cooke; Rev. Sci. Instrum., 78, 096106 (2007) To Diff. Pump

Perfluoropropanoic acid Trifluoroacetic acid S. Antolinez, J.L. Alonso, H. Dreizler, E. Hentrop, D.H. Sutter; Z. Naturforsch. 54a, 524, (1999) B. Ouyang, T.G. Starkey, B.J. Howard; J. Phys. Chem. A., 111, 6165 (2007) Perfluoropropanoic acid G.S. Grubbs II, A. Serrato III, D. A. Obenchain, S.A. Cooke, S.E. Novick, W. Lin; J. Mol. Spec., 275, 1(2012). G.S. Grubbs II, D.A. Obenchain, D.S. Frank, S.E. Novick, S.A. Cooke, A. Serrato III, W. Lin; J. Phys. Chem. A., 119, 10475 (2015) Perfluorobutyric acid (& its monohydrate) J. Thomas, A. Serrato III, W Lin, W. Jäger, Y. Xu; Chem. Eur. J., 20, 6148, (2014) Perfluoropentanoic acid A.M. Pejlovas, W. Lin, S.G. Kukolich; J. Chem. Phys., 143, 124311 (2015) One lower energy conformer detected for perfluorocarboxylic acids Difluoroacetic acid B.P. van Eijck, A.A.J. Maagdenberg, G. Janssen, T.J. van Goethem-Wiersma; J. Mol. Spec., 98, 282 (1983) Fluoroacetic acid B.P. van Eijck, P. Brandts, P.M. Maas; J. Mol. Strc., 44, 1 (1978) B.P. van Eijck, G. Van der Plaats, P.H. Van Roon; J. Mol. Spec., 11, 67 (1971) Two conformers detected for short partially fluorinated carboxylic acids

3,3,3-trifluoro-2-(trifluoromethyl)propanoic acid PES’ partially fluorinated carboxylic acids chains multiple conformers 3,3,3-trifluoro-2-(trifluoromethyl)propanoic acid J. Thomas, M.J. Carrillo, A. Serrato III, E.G. Schnitzler, W. Jäger, Y. Xu, W. Lin; Chem. Phys. Lett., 661, 210 (2016) Two lower energy conformers observed 2,3,3,3-tetrafluoropropanoic acid Lin et al. Investigation ongoing Three conformers observed 3,3,3-trifluoropropanoic acid L. Evangelisti, J. van Wijngaarden; J. Mol. Spec., 290, 1 (2013) One lower energy conformer observed

4,4,4-Trifluorobutyric acid conformational landscape Original B3LYP / aug-cc-pVTZ to expected major conformer Dihedral τ(OO=C-C1-C2-C3) in 5° increments @ B3LYP / aug-cc-pVTZ Minima structures further optimized @ MP2 / aug-cc-pVTZ Higher energy conformers with dihedrals of 124° and -124° C1 C2 C3 C4 Conformer I Conformer II 0.48 kJ mol-1 Conformer I C1 C2 C3 C4

4,4,4-Trifluorobutyric acid Conformer 1 C1 C2 C3 C4 Conformer 2 Dimer? 6 ← 5 7 ← 6 8 ← 7 5 ← 4 9 ← 8 Frequency /MHz Intensity /V 1.5 bar Ar bubbled through sample 7200 averages

4,4,4-Trifluorobutyric acid Conformer 1 Dimer? “New” 6 ← 5 7 ← 6 8 ← 7 5 ← 4 9 ← 8 Frequency /MHz Intensity /V 1.5 bar Ar bubbled through sample 7200 averages

4,4,4-Trifluorobutyric acid Conformer 2? Experimental Conformer 2: Fit of 3 possible transitions, to be verified Conformer 2: Spectral prediction Conformer 1: Spectral Fit Frequency /MHz Conformer 1 Conformer 2 MP2 aug-TZ Experiment Speculation* Bbar/MHz 728.9 724.5 743.75 743.12 *Preliminary results based on 3 transitions at 2:1 intensity

4,4,4-Trifluorobutyric acid Spectroscopic constants B3LYP/ aug-cc-pVTZ MP2/ Experimental A0 /MHz 3628.3 3640.3 3649.20(33) B0 /MHz 739.15 751.87 746.74870(64) C0 /MHz 694.90 706.02 702.21650(64) J /kHz - 0.0200(44) JK /kHz 0.384(13) Paa/(uǺ2) 635.86 624.57 628.99 Pbb/(uǺ2) 91.42 91.24 90.71 Pcc/(uǺ2) 47.88 47.59 47.79 N 33 /kHz 7 Planar moment of inertia: Paa = (Ib +Ic – Ia)/2, Pbb = (Ia +Ic – Ib)/2, and Pcc = (Ia +Ib - Ic)/2. Watson Ir in Pickett

4,4,4-Trifluorobutyric acid ··· formic acid 8-12 GHz Two conformers 86 a-type transitions No splitting's associated with hydrogen exchange Frequency /MHz

4,4,4-Trifluorobutyric acid ··· formic acid Conformer A Conformer B 4,4,4-Trifluorobutyric acid monomer conformers Conformer 1 Conformer 2

4,4,4-Trifluorobutyric acid-formic acid Conformer A Conformer B B3LYP MP2 Experimental ΔD /kJ mol-1 - 4.0 ΔD0 /kJ mol-1 3.6 3.9 A0 /MHz 2523.1 2514.7 2517.80(17) 2666.4 2673.0 B0 /MHz 285.09 289.58 287.49357(12) 281.48 285.48 C0 /MHz 269.21 273.03 271.34761(12) 267.50 271.11 ΔJ /kHz 0.00510(22) ΔJK /kHz 0.0380(17) ΔK /kHz 120(52) µa /D 1.7 µb /D 0.3 0.4 µc /D 0.0

Manifestation of proton tunneling 1/2 Formic acid dimer O. Birer, M. Havenith; Annu. Rev. Phys. Chem., 60, 263 (2009) & refs. Malonaldehyde W.F. Rowe, R.W. Duerst, E.B. Wilson; J. Am. Chem. Soc., 98, 4021 (1976) S.L. Baughcum, R.W. Duerst, W.F. Rowe, Z. Smith, E.B Wilson; J. Am. Chem. Soc., 103, 6296 (1981) S.L. Baughcum, Z. Smith, E.B. Wilson, R.W. Duerst; J. Am. Chem. Soc., 106, 2260 (1984) P. Turner, S.L. Baughcum, S. L. Coy, Z. Smith; J. Am. Chem. Soc. 106, 2265 (1984) Tropolone K. Tanaka, H. Honjo, T. Tanaka, H. Kohguchi, Y. Ohshima, Y. Endo; J. Chem. Phys., 110, 1969 (1999) J.C. Keske, W. Lin, W.C. Pringle, S.E. Novick, T.A. Blake, D.F. Plusquellic; J. Chem. Phys., 124, 074309 (2006) Propriolic acid ··· Formic Acid A.M. Daly, P.R. Bunker, S.G. Kukolich; J. Chem. Phys., 132(20), 201101/1 (2010) A.M. Daly, P.R. Bunker, S.G. Kukolich; J. Chem. Phys., 133(7), 079903/1 (2010) A.M. Daly, K.O. Douglass, L.C. Sarkozy, J.L. Neill, M.T. Muckle, D.P. Zaleski, B.H. Pate, S.G. Kukolich; J. Chem. Phys., 135, 154304/1 (2011) Benzoic Acid ··· Formic Acid L. Evangelisti, P. Ecija, E.J. Cocibero, F. Castano, A. Lessarri, W. Caminati, R. Meyer; J. Phys. Chem. Lett., 3, 3770 (2012)

Manifestation of proton tunneling 2/2 Formic acid ··· acetic acid M.C.D. Tayler, B. Ouyang, B.J. Howard; J. Chem. Phys., 134, 054316/1 (2011) Acrylic acid ··· Trifluoroacetic acid (cis & trans) Q. Gou, G. Feng, L. Evangelisti, W. Caminati,; J. Phys. Chem. A., 117, 13500 (2013) Acrylic acid ··· Difluoroacetic acid G. Feng, Q. Gou, L. Evangelisti, W. Caminati; Angew. Chem. Int. Ed., 53, 530 (2014) Perfluorobutyric acid ··· formic acid J. Thomas, A. Serrato III, M.J. Carrillo, W. Lin, W. Jäger, Y. Xu; J. Mol. Spectrosc., 335, 88 (2017) 2.759 MHz 1.203 MHz 303 313 1.877 MHz 2.806 MHz 12 kHz No Tunneling No Tunneling

4,4,4-Trifluorobutyric acid PES landscape determined One conformer observed Analogous to 3,3,3-trifluoropropionic acid1 4,4,4-Trifluorobutyric acid-formic acid complex No splittings associated with hydrogen exchange Two conformers calculated 2nd conformer that would be formed by proton exchange not observed First measurement 1 L. Evangelisti, J. van Wijngaarden; J. Mol. Spec., 290, 1 (2013)

National Science Foundation Wesleyan Chemistry Department FB02 WE10 Wei Lin Stewart Novick Steve Cooke Karen Peterson Pete Pringle Wilman Orellana Yoon Choi Angela Chung Eric Arsenault Robert Melchreit National Science Foundation Wesleyan Chemistry Department FB02 WE10 TI11 FB06 Not pictured: Robert Melchreit TC02 Karen Peterson: RH07