Accurate Equilibrium Structures of Piperidine and Cyclohexane JEAN DEMAISON, Laboratoire de Physique de Lasers, Atomes et Molécules, Université de Lille.

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Accurate Equilibrium Structures of Piperidine and Cyclohexane JEAN DEMAISON, Laboratoire de Physique de Lasers, Atomes et Molécules, Université de Lille 1, Villeneuve d’Ascq Cedex, France NORMAN C. CRAIG, Department of Chemistry and Biochemistry, Oberlin College, Oberlin, OH USA PETER GRONER, Department of Chemistry, University of Missouri – Kansas City, Kansas City, MO USA PATRICIA ÉCIJA and EMILIO J. COCINERO, Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV-EHU), Ap. 644, E Bilbao, Spain ALBERTO LESARRI, Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, E Valladolid, Spain HEINZ DIETER RUDOLPH, Department of Chemistry, University of Ulm, D Ulm, Germany

Piperidine C s symmetry 25 parameters Cyclohexane D 3d symmetry 6 parameters

MW Transitions for Isotopologues of Piperidine Species Transitions LiteratureNewTotal normal79 a,b C 1 32 c C 1 13 c C 1 11 c N 4 4 ND 7 b.d 7 a Parkin, J. E.; Buckley, P. J.; Costain, C. C. J. Mol. Spectrosc. 1981, 89, b Ehrlichmann, H.; Grabow, J.-U.; Dreizler, H.; Heineking, N.; Andolfatto, M. Z. Naturforsch. A 1989, 44, c Spoerel, U.; Stahl, W. Chem. Phys. 1998, 239, d Using frequencies deperturbed for quadrupole coupling. 24 rotational constants fit to transitions with initial centrifugal distortion constants computed with the MP2/cc-pVTZ model.

MW Transitions for Piperidine

MW Transitions for Isotopologues of Cyclohexane SpeciesTransitions Literature a 1,1-d C 1 -1,1-d d 1 -eq 39 1-d 1 -ax 7 1,1,2,2,3,3-d a Dommen, J.; Brupbacher, Th.; Grassi, G.; Bauder, A.. J. Amer. Chem. Soc. 1990, 112, One rotational constant (A 0 = B 0 ) found for the d 0 and d 12 species by rotational Raman spectroscopy. b One rotational constant found for the d 0 species by Raman coherence spectroscopy. c b Peters, R. A.; Walker, W. J.; Weber, A. J. Raman Spectrosc. 1973, 1, C Brügger, G.; Frey, H.-M.; Steinegger, P.; Kowalewski P.; Leutwyler, S. J. Phys. Chem. A 2011, 115,

Equilibrium Rotational Constants From GS rot. consts. with adjustments for vib-rot interaction (MP2/cc- pVTZ) and a small electronic contribution [B3LYP/6-311+G(3df,2pd)] Predicate Structures Piperidine and Cyclohexane r e = r{CCSD(T)/cc-pVTZ(FC) + MP2/[cc-pVQZ(FC) – cc-pVTZ(FC) + cc-pwCVQZ(AE) – cc-pwCVQZ(FC)} Cyclohexane – in close agreement r e = r{CCSD(T)/cc-pwCVTZ(AE) + MP2/[cc-pwVQZ(AE) – cc-pVTZ(AE)]} Mixed Estimation Concurrent fit to equilibrium rotational constants and predicate structural parameters, each set with appropriate uncertainties.

Structure Fitting Detects Faulty MW Assignments through poor fit of some rotational constants Pip C 1 Pip C 1 lines for lines for 3 03 – 2 02 ca MHz (lit.) ca MHz (lit.) P b = Σ m i b i 2 P b (pred) = u Å 2 P b (obs) = u Å 2

Comparative Bond Lengths/Å PiperidineCyclohexane N-H1.012 N-C C2-Hx1.102 C2-Hq1.090 C2-C C3-Hx1.092 C3-Hq1.091 C3-C C4-Hx C4-Hq1.091

Conclusions Improved MW observations for isotopologues of piperidine. Equilibrium structures for piperidine and cyclohexane (0.001 Å, 0.2°). Structure fitting detects faulty MW assignments. Impact of nitrogen atom substitution on the bond parameters in cyclohexane.

Acknowledgments Ohio Supercomputer Center. Oberlin College. Spanish MICINN and MINECO (CTQ , CTQ ). Basque Government (IT520-10) and UPV/EHU (UFI 11/23). Research facilities from the SGI/IZO-SGIker.