Joseph A. Fournier, Robert K. Bohn, John A. Montgomery, Jr. University of Connecticut, Storrs, CT Microwave Spectroscopy and Structures of Perfluorohexane.

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Joseph A. Fournier, Robert K. Bohn, John A. Montgomery, Jr. University of Connecticut, Storrs, CT Microwave Spectroscopy and Structures of Perfluorohexane and 1H-heptafluoropropane

M. D’Amore, et. al., J. Am. Chem. Soc. 128(2006)1099. C. Sperati, H. Starkweather, Jr. Fortcher. Hochpolym. Forsch. 2(1961)465

} d ρ θ τ 2345 φ r T. Shimanouchi, S. Mizushima. J. Chem. Phys. 23(1955)707. M. Iwasaki. J. Polym. Sci. A-1 (1963)1099. Helical Perspective Molecular Perspective

Helical vs. Dihedral Angle Helical Perspective (X-ray crystallographers) Molecular Perspective ρ – distance from each atom to the helix axis r – CC bond length θ – angle of rotation about the helix axis φ – CCC bond angle d – pitch; translation along the helix axis τ – CCCC dihedral angle Helix parameters as functions of molecular parameters: cosθ = ½[ - cosφ + cosτ - cosφ cosτ - 1] d 2 = r 2 (1 - cosτ)(1 - cosφ)/(3 + cosφ - cosτ + cosφ cosτ) ρ 2 = 2r 2 (1 + cosφ)/(3 + cosφ - cosτ + cosφ cosτ) 2 Molecular parameters as functions of helical parameters: r 2 = d 2 + 4ρ 2 sin 2 (θ/2) cos(φ/2) = (1 - d 2 /r 2 ) 1/2 sin(θ/2) tan(τ/2) = (d/r) tan(θ/2)

b a c Top view, Helical Twist, C 2 symmetry Perfluoropentane, C 5 F 12 J.A. Fournier, R.K. Bohn, J.A. Montgomery, Jr., M. Onda. J. Phys. Chem. A 114 (2010) 1118.

Pentane (C 5 H 12 ), all bonds trans (180 O ), C 2v symmetry C 5 F 12, bonds twisted from trans by 17 O, C 2 symmetry

Perfluorohexane, C 6 F 14 Hexane (C 6 H 14 ), C 2h C 6 F 14, C 2, ~17 o twist a b c

Observed Spectroscopic Constants A/MHz (9) B/MHz (8) C/MHz (10) D J /kHz0.0691(4) P aa /uÅ P bb /uÅ P cc /uÅ Kappa No. Lines46 Std. Dev./kHz1.8

Scaling the Calculated Model Scale the principal coordinates of each atom from the PBE0/VTZ calculations by the factor (P ii obs / P ii PBE0) 1/2 Scaling Factors: (a), (b), (c). Calculate structural parameters from new coordinates. Obs'dPBE0/VTZ Scaled PBE0/VTZ A/MHz B/MHz C/MHz P aa /uÅ P bb /uÅ P cc /uÅ

Scaled Structure PBE0/VTZ Scaled PBE0/VTZ C 1 -C C 2 -C C 3 -C / C 1 C 2 C / C 3 C 4 C C1C2C3C4C1C2C3C C2C3C4C5C2C3C4C5 18.0

1H-heptafluoropropane HCCC Trans HCCC Gauche J.A. Fournier, R.K. Bohn. Dalton Trans. 39(2010) 4575.

Perfluoropropane, C 3 F 8 PBE0/VTZ computations predict a non-helical, C 2v structure. The computed spectroscopic constants are in excellent agreement with the observed. J.A. Fournier, R.K. Bohn, J.A. Montgomery, Jr., M. Onda. J. Phys. Chem. A 114 (2010) 1118.

Observed Spectroscopic Constants GaucheTrans A/MHz (7) (10) B/MHz (4) (19) C/MHz (5) (20) Δ J /kHz0.0691(4)0.0938(20) Δ JK /kHz0.0315(11)0.763(10) Δ K /kHz0.0378(14)-0.758(8) δ J /kHz (19)0.0092(18) δ K /kHz-0.238(3)-1.12(8) Kappa No. Lines7138 a-types812 b-types1826 c-types450 Std. Dev./kHz1.11.7

Dipole Moments Compound Predicted Dipole/DDihedral C 4 F o C 5 F o C 6 F o o o Trans 1H-HFP0.47o7o 0.23o3o 0.061o1o

Scaling the Calculated Model Scale the principal coordinates of each atom from the PBE0/VTZ calculations by the factor (P ii obs / P ii PBE0) 1/2 Scaling Factors: (a), (b), (c) for gauche form. Calculate structural parameters from new coordinates. Obs'dPBE0/VTZ Scaled PBE0/VTZ Obs'dPBE0/VTZ Scaled PBE0/VTZ A/MHz B/MHz C/MHz P aa /uÅ P bb /uÅ P cc /uÅ Gauche Trans

Scaled Structures Gauche Trans PBE0/VTZScaled PBE0/VTZScaled C 1 -C C 2 -C / C 1 C 2 C HC 1 C 2 C F4C1C2C3F4C1C2C F9C3C2C1F9C3C2C

Summary The microwave spectra of the C 2 structure of perfluorohexane and the gauche and trans conformers of 1H-heptafluoropropane have been observed and assigned. The dihedral angles of C 6 F 14 are ~17-18 o away from trans. No c-type transitions were observed for the trans form, indicating an ab-plane of symmetry or an insufficient twist. Structural analysis was performed by scaling the calculated models to reproduce the observed spectroscopic constants.

Acknowledgments At UConn: Prof. Harvey Michels, James Dombrowski, Congtin Phan. At Wesleyan : Prof. Stewart Novick, Prof. Pete Pringle, Dr. Andrea Minei, Dan Frohman. Measurements were performed on the pulse-jet Fourier Transform Microwave Spectrometer of the Southern New England Microwave Consortium at Wesleyan University.