Spectroscopic Characterization of the Hydrates of Some ...

Perfluorobutyric acid and its monohydrate: a chirped pulse and cavity based Fourier transform microwave spectroscopic study Javix Thomasa, Agapito Serratob, Wei Linb, Wolfgang Jgera, and Yunjie Xua Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada, T6G 2G2 Department Chemistry and Environmental Sciences, The University of Texas at Brownsville, Brownsville, TX 78520 a b 69th International Symposium on Molecular Spectroscopy, 06/18/14 The ground-state structures of (a) HCl-H2O, (b) HNO3-H2O, (c) H2SO4H2O, and (d) HNO3-(H2O)2, all determined by rotational spectroscopy The monohydrate, dihydrate and trihydrate of trifluoroacetic acid Ouyang et al J. Phy. Chem. 111 (2007) 6165-6175

The perfluobutyric acid (PFBA) Experiment University of Alberta chirped-pulse and cavity Fourier transform microwave spectrometers. Scan range between 8 and 16 GHz (chirped-pulse) and 6 and 26 GHz (cavity). Perfluorobutyric acid (98% Aldrich). Helium

(Neon) expansion gas at 2-6 bars backing pressure. Line position error 50 kHz. The Chirped-pulse FTMW [email protected] The Chirped-pulse FTMW spectrometer at the University of Alberta A portion of the spectrum of Perfluorobutyric Acid. Comparison of the most stable conformers

of the three short chain PFCAs Another conformer of Perfluorobutyric Acid? Ellis et al J. Phy. Chem. 108 (2004) 10099-10106 A potential energy scan by rotating carboxyl group about the C1-C2 bond, i.e. dihedral angle O4-C1-C2-C3, in steps of 15 degree at the MP2/6-311++G(2d,p) level Spectroscopic constants Paramete PFBA PFBA(D) PFBA--H2O A (MHz) 1398.67932(9) 1391.2579(6) 1310.1124(1) B (MHz) 624.63715(5) 615.58678(8) 406.23021(6)

C (MHz) 598.42482(4) 588.84980(7) 390.90242(5) DJ (kHz) 0.0221(3) 0.0206(4) 0.0181(1) DJK (kHz) 0.012(2) 0.047(8) -0.0437(9) DK (kHz) 0.041(3) 0.041(3)[c] 0.369(3) d1 (kHz) -0.0012(2) -0.0012(2)[c] -0.0011(1) d2 (kHz) -0.0012(2)

-0.0014(2) -0.00023(9) N 102 40 114 (kHz) 1.4 2.1 1.9 Centrifugal distortion constants of the first four perfluocarboxylic acids CF3COOH a CF3CF2COOHb

CF3CF2CF2COOH CF3CF2CF2COOHc DJ /kHz 0.9660(217) 0.245(4) 0.0221(3) 0.003(1) DJK /kHz -0.938(62)

0.40(2) 0.012(2) N/A DK /kHz 0.466(61) -0.44(1) 0.041(3) 0.26(5)

d1 /kHz -0.0483(69) 0.012(3) -0.0012(2) N/A d2 /kHz 0.3471(51) -4.3(1) -0.0012(2)

N/A a Ouyang et al J. Phy. Chem. 111 (2007) 6165. b Grubbs et al J. Mol. Spectrosc. 275 (2012) 1. c Pejlovas et al submitted to Chem. Phys. Lett. Perfluorobutyric acid-water complex Optimized geometry at the B3LYP/6-31G* level with fixing the intrageometry of each monomer. Urata et al Phy. Chem. Chem. Phy. 6 (2004) 3325-3332 Perfluorobutyric acid-water complex

Parameter De[a] PFBA--H2O-I 0 PFBA--H2O-II 0.11 PFBA--H2O-III 32.3 D0[a] 0 0.07

28.7 A 1305 1305 878 B 410 410

586 C |a| 395 395 476 2.90 3.70 0.60

|b| 1.81 0.06 3.30 |c| 0.99 0.58 0.44 Spectroscopic constants

Paramete PFBA PFBA(D) PFBA--H2O A (MHz) 1398.67932(9) 1391.2579(6) 1310.1124(1) B (MHz) 624.63715(5) 615.58678(8) 406.23021(6) C (MHz) 598.42482(4) 588.84980(7) 390.90242(5) DJ (kHz) 0.0221(3) 0.0206(4) 0.0181(1) DJK (kHz) 0.012(2) 0.047(8) -0.0437(9) DK (kHz) 0.041(3)

0.041(3)[c] 0.369(3) d1 (kHz) -0.0012(2) -0.0012(2)[c] -0.0011(1) d2 (kHz) -0.0012(2) -0.0014(2) -0.00023(9) N 102 40 114 (kHz) 1.4 2.1 1.9

Conclusion High resolution rotational spectra of PFBA and its monohydrate were studied for the first time using chirped pulse and cavity based Fourier transform spectroscopies. One PFBA conformer and One PFBA monohydrate conformer were conclusively identified experimentally. This monohydrate conformer was shown to behave well as a semirigid rotor and adopt a unique orientation for the nonbonded water H atom, in contrast to other smaller acid--water complexes studied using rotational spectroscopy where large amplitude motions and tunnelling motions are significant. Javix Thomas et. al. Chem. Eur. J. 20(20) (2014) 6148 Acknowledgement The University of Alberta and the Natural Sciences and Engineering

Research Council (NSERC) of Canada for WJ or YX Olegario Vazquez Rana Faculty Fellowship, UT Brownsville and the Welch Foundation for WL

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