The Equilibrium C–Cl,C–Br,and C–I Bond Lengths from Ab Initio Calculations,Microwave and Infrared Spectroscopies,and Empirical Correlations

The equilibrium structures of a few small molecules containing halogens: methyl halides, cyanogen halides, haloethynes, and halocyanoethynes (from chloride to iodide) are reviewed and redetermined if necessary using high-level ab initio calculations and experimental data from microwave and infrared spectroscopies. The correlation of the r(C–X) (X=Cl, Br, I) bond length with other properties (electronegativity or another bond length) is analyzed. It is shown that simple empirical correlations may be used to make a reliable prediction of the r(C–X) bond length.     

Microwave spectrum,centrifugal distortion,internal rotation and excited torsional states of isobutene

The microwave spectrum of isobutene has been recorded from 10 to 35 GHz. From the analysis of the ground and first two excited torsional state splittings, the following internal rotation parameters were calculated: V₃ = 2170 cal mol.^?1, V'₁₂ = ?210 cal. mol.^?1, I_α = 3.18amu Ų and angle (methyl-top to b-axis) 58.21°. Centrifugal distortion parameters were also obtained for the ground state.     

Structural and conformational properties of 1,2-propadienylphosphine (allenylphosphine) studied by microwave spectroscopy and quantum chemical calculations

1,2-Propadienylphosphine (allenylphosphine), H(2)C=C=CHPH(2), has been investigated by Stark and Fourier transform microwave spectroscopy. Two rotameric forms denoted syn and gauche have been assigned. The syn form has a symmetry plane (C(s)() symmetry) where the lone electron pair of phosphorus points toward the double bonds. The phosphino group is rotated roughly 120 degrees from this position in the gauche rotamer. The dipole moment of syn was determined to be mu(a) = 1.613(23), mu(b) = 2.347(24), mu(c) = 0 (for symmetry reasons), and mu(tot) = 2.848(28) x 10(-30) C m [0.854(8) D]. The energy difference between the two forms was found to be 2.1(4) kJ/mol from relative intensity measurements with syn as the more stable conformer. Extensive quantum chemical calculations have been carried out and accurate equilibrium structures have been determined for these two rotamers, as well as for the corresponding two conformers of vinylphosphine (H(2)C=CHPH(2)).     

Assignments of submillimeter emissions in difluoromethane pumped by12C18O2 and12C18O2 lasers

A FT spectrum of ₃, ₉ and ₇ of CH₂F₂ is recorded and assigned between 1030 and 1230 cm^–1. Coincidences with CO₂ lasers are investigated.Submillimeter emissions are unambiguously assigned by a loop procedure including only IR and SMM measurements. In some cases pseudo-loops are added using ground state computed energies. In spite of the large perturbations, an exact model for excited vibrational states is not needed to ascertain SMM assignments.     

Microwave spectrum of dimethylallene : Centrifugal distortion analysis

The rotational absorption lines of the molecule dimethylallene in the vibrational ground state deviate from a rigid rotor pattern by shifts due to centrifugal distortion and by shifts and splittings due to methyl top internal rotation. By enlarging the number of previously measured lines it has been possible to apply successfully a Watson-type centrifugal distortion formula and to analyze the resulting “effective rigid rotor” rotational constants for the remaining contributions due to internal rotation and centrifugal distortion. Care has been taken to calculate or at least estimate the separate contributions and compare their magnitudes.     

Why it is sometimes difficult to determine the accurate position of a hydrogen atom by the semiexperimental method: Structure of molecules containing the OH or the CH3 group

The semiexperimental (SE) technique, whereby equilibrium rotational constants are derived from experimental ground‐state rotational constants and corrections based on an ab initio cubic force field, has the reputation to be one of the most accurate methods to determine an equilibrium structure ( ). However, in some cases, it cannot determine accurately the position of the hydrogen. To investigate the origins of this difficulty, the SE structures of several molecules containing either the OH or the CH₃ group are determined and compared to their best ab initio counterparts. It appears that an important factor is the accuracy of the geometry used to calculate the force field, in particular when the least‐squares system is not well conditioned. In this case, the mixed regression method is often an easy way to circumvent this difficulty. © 2014 Wiley Periodicals, Inc.     

The ν6=1 state of fluoroform, HCF3: analysis of the rotational and vibrational spectra

An analysis of the ν₆=1 state of fluoroform is performed using rotational and high resolution infrared spectra. Previously radiofrequency data [Chem. Phys. Lett. 214 (1993) 265–270] and millimeter data [J. Mol. Spectrosc. 131 (1988) 1–8] were combined with new millimeter and infrared measurements, and a set of 27 parameters has been derived. A multiple fit analysis was performed confirming the assumption that the ν₆=1 excited state is not affected by intervibrational resonances.     

Equilibrium structures of heterocyclic molecules with large principal axis rotations upon isotopic substitution

Equilibrium structures, r(e), of the heterocyclic molecules oxirane, furazan, furan, ethylene ozonide, and 1,3,4-oxadiazole have been determined using three different, somewhat complementary techniques: a completely experimental technique (r(m)), a semiexperimental technique (r(e)(SE), whereby equilibrium rotational constants are derived from experimental effective ground-state rotational constants and corrections based principally on an ab initio cubic force field), and an ab initio technique (r(e)(BO), whereby geometry optimizations are usually performed at the coupled cluster level of theory including single and double excitations augmented by a perturbational estimate of the effects of connected triple excitations [CCSD(T)] using quadruple-ζ Gaussian basis sets). All these molecules are asymmetric tops with the moment of inertia I(c) much larger than the other two moments of inertia, I(a) and I(b). Molecules of this shape experience a large rotation of the principal axis system upon certain isotopic substitutions. For such isotopologues it is difficult to obtain a good structural fit to the semiexperimental moments of inertia I(a) and I(b), which may significantly reduce the accuracy of the r(e)(SE) structural parameters. The origin of this difficulty is explained. For the heavy-atom skeleton of these molecules it was possible to determine a rather accurate empirical mass-dependent structure without a priori knowledge of the equilibrium structure.     

Breakdown of the reduction of the rovibrational Hamiltonian: The case of SO2F2

The ground state rotational spectrum of the near-spherical top molecule S¹⁸O₂F₂ (sulfuryl fluoride) has been measured from 50 to 700 GHz. As for the parent isotopologue, S¹⁶O₂F₂ [K. Sarka, J. Demaison, L. Margulès, I. Merke, N. Heineking, H. Bürger, H. Ruland, J. Mol. Spectrosc. 200 (2000) 55-64], it was necessary to use a non-reduced Hamiltonian in order to obtain a satisfactory fit. It was possible to determine six quartic centrifugal distortion constants (instead of five for a standard asymmetric top) and five sextic constants (one of them not existing in the reduced Hamiltonian) could also be determined. This ground state level has also been analysed thanks to a tensorial formalism developed in Dijon. Only two tensorial sextic constants are fixed to zero, all others have been adjusted. Although S¹⁸O₂F₂ is less spherical than S¹⁶O₂F₂, the analysis was more difficult. It is partly due to the fact that S¹⁸O₂F₂ is oblate whereas S¹⁶O₂F₂ is prolate. The experimental quartic centrifugal distortion constants were found in good agreement with those calculated from the force field, confirming the correctness of the analysis.