72nd International Symposium on Molecular Spectroscopy, 6/20/2017

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72nd International Symposium on Molecular Spectroscopy, 6/20/2017 CONFORMATIONAL ANALYSIS OF 3,3,3-TRIFLUORO-2-(TRIFLUOROMETHYL) PROPANOIC ACID JAVIX THOMAS, Department of Chemistry, University of Alberta, Edmonton, AB, Canada; MICHAEL J CARRILLO, AGAPITO SERRATO III, Department of Chemistry, University of Texas Rio Grande Valley, Brownsville, TX, USA; ELIJAH G SCHNITZLER, WOLFGANG JÄGER, YUNJIE XU, Department of Chemistry, University of Alberta, Edmonton, AB, Canada; WEI LIN, Department of Chemistry, University of Texas Rio Grande Valley, Brownsville, TX, USA. 72nd International Symposium on Molecular Spectroscopy, 6/20/2017

Only one lower energy conformer detected for perfluorocarboxylic acids 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). Perfluorobutyric acid 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; Chem. Phys. Lett., 143, 124311 (2015)

Comparison of the most stable conformers of the three short chain PFCAs, i.e. trifluoroacetic acid (left), perfluoropropionic acid (middle), and PFBA (right).

A potential energy scan of perfluorobutyric acid by rotating carboxyl group about the C1-C2 bond

2,3,3,3-tetrafluoropropanoic acid Difluoroacetic acid B.P. van Eijck, A.A.J. Maagdenberg, G. Janssen, T.J. van Goethem-Wiersma; J. Mol. Spec., 98, 282 (1983) 2 conformers observed 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) 2,3,3,3-tetrafluoropropanoic acid Lin et al. Investigation ongoing 3 conformers observed 3,3,3-trifluoropropanoic acid L. Evangelisti, J. van Wijngaarden; J. Mol. Spec., 290, 1 (2013) One lower energy conformer 4,4,4-trifluorobutyric acid Yoon Jeong Choi, Alex Treviño, Susanna L. Stephens, Stephen A. Cooke, Stewart E. Novick, Wei Lin; WD04

3,3,3-trifluoro-2-(trifluoromethyl)propanoic acid (TTPA)

The microwave spectrometers @Edmonton Chirped-pulse FTMW spectrometer Cavity based FTMW spectrometer

The Chirped-pulse FTMW spectrometer@Edmonton

Experiment University of Edmonton chirped pulse and cavity based Fourier transform microwave spectrometers; TTPA(97% Sigma Aldrich) in gas inlet; Trace amount of TTPA in expansion gas of 3 bar Helium (chirped pulse) and 2 bar Neon (cavity based).

Theory Gaussian 09 program package dihedral angle τ(O12-C5-C2-C1) scan at B3LYP/6-311G level; Structure optimizations at B3LYP/aug-cc-pVTZ level and MP2/aug-cc-pVTZ level.

Potential energy scan along the dihedral angle τ(O12-C5-C2-C1) in steps of 10° The calculations were done at the B3LYP/6-311G level.

Geometries of the four TTPA conformers identified computationally

Calculated relative dissociation energies and spectroscopic constants TTPA-I TTPA-II TTPA-III TTPA-IV Parameters B3LYP MP2 ΔD (kJ/mol) 0.48 0.42 14.3 13.9 23.5 23.0 ΔD0 (kJ/mol) 0.36 0.27 13.6 22.9 22.6 A (MHz) 1063.6 1078.1 1073.5 1087.8 1074.5 1087.5 1129.1 1146.6 B (MHz) 963.0 977.1 962.7 977.2 965.4 979.7 952.6 967.4 C (MHz) 680.5 692.6 684.9 696.6 688.1 699.2 656.9 670.5 µa (Debye) 0.0 2.0 1.8 µb (Debye) 1.9 1.0 1.2 1.3 µc (Debye) 2.2 2.1 0.6 0.5 0.7 2.8

A sample spectrum showing the 440-331 transition of TTPAI and 441-331 transition of TTPA II from the cavity based measurement.

Experimental spectroscopic constants Parameter TTPA-I TTPA-II A (MHz) 1075.53107(56) 1085.63313(37) B (MHz) 975.17899(41) 975.16102(34) C (MHz) 688.28340(34) 692.86057(21) ΔJ (kHz) 0.0359(73) 0.0396(60) ΔJK (kHz) 0.730(31) 0.402(23) ΔK (kHz) -0.724(21) -0.394 (16) δJ (kHz) 0.0114(26) 0.0131(27) δK (kHz) 0.029(10) -0.0385(79) N 37 36 σ (kHz) 2.8 1.7

Conclusion The rotational spectrum of TTPA was measured for the first time using both chirped-pulse and cavity-based FTMW spectrometers. Two conformers were observed experimentally and identified unambiguously. The rotational constants of the observed conformers are in excellent agreement with those from the quantum chemical structures. Comparison of TTPA and previously reported fluorinated carboxylic acids shows some noticeable differences in their preferred geometries and conformational energetics, such as the interconversion barrier height between the conformers, highlighting the diversity of conformational landscapes in this class of compounds.

Acknowledgement Welch Foundation # BX-0048 UTRGV Undergraduate Research Initiative (URI) The University of Alberta The Natural Sciences and Engineering Research Council (NSERC) of Canada YX and WJ are holders of Tier I Canada Research Chairs. Texas Advanced Computing Center (TACC) and the Shared Hierarchical Academic Research Computing Network (SHARCNET: www.sharcnet.ca), the Western Canada Research Grid (Westgrid), and Compute/Calcul Canada.