Molecular Structure of Phenylphosphine and Its Analogs by Gas-Phase Electron Diffraction and Quantum-Chemical Calculations

The molecular structures of phenylphosphine and its analogs, aniline and phenylarsine, were studied by gas-phase electron diffraction and quantum-chemical methods. The geometry and force constants were calculated at the HF/6-31G and B3LYP/6-31G^* levels of theory. Phenylphosphine and phenylarsine possess a bisector conformation with asymmetric phenyl rings. The main geometric parameters are as follows (r _a): P-C 1.833(6), C-Cav 1.397(1)Å. The structures of molecules like X₂YPh (X = H, F, Cl; Y = N, P, As) were discussed.     

Molecular structure of gaseous vanadyl(V) fluoride as studied by electron diffraction,and its modified valence force field

The molecular structure of gaseous OVF₃ has been determined by electron diffraction to be: r_g(V-O) = 1.570(5) Å, r_g(V-F) = 1.729(2) Å and ∠_α(OVF) = 107.5(4)°. A modified force field has been fitted to results from spectroscopic as well as diffractional studies. A similar attempt to determine the force field for OVCl₃ was not as successful as for OVF₃, probably because the Coriolis constants are less accurately determined for that molecule.     

New approach to the nonparametric determination of the internal rotation potential from electron diffraction data. Reinvestigation ofm-bromonitrobenzene

A numerical algorithm for the nonparametric determination of the internal rotation potential from electron diffraction data using Tikhonov's regularization method is described. The range of admissible values of the regularization parameter is estimated using Hamilton's statistical criterion. m-Bromonitrobenzene was reinvestigated using this approach. It was found that the form of the potential may be reliably established only in the region of the minimum corresponding to the planar conformation of the molecule. Fourier series approximation of the experimental values of the potential in the region of the minimum gives the rotation barrier of 4.6–5.4 kcal/mole. The following basic geometrical parameters have been obtained (r_a in Å, ∠_α in deg, the error equals triple standard deviation): r(C?C)_ave=1.399(3), r(C?N)=1.459(16), 1.459(16), r(N=O)=1.244(3), r(C?Br)=1.884(6), r(C?H)=1.099(20), ∠CC_NC=123.9(1.4), ∠C_NCCBr=116.8(1.5), ∠C_NCC=116.6(1.9), ∠CNO=118.8(0.8). The results are compared with the data for the related compounds.     

Molecular Structure of Triphenylamine in the Gas Phase

The molecular structure of triphenylamine was studied by gas-phase electron diffraction in combination with ab initio calculations. It is found that in the gas phase at 160°C the molecule possesses C₃ symmetry. The principal geometric parameters are as follows (r _a structure): N-C 1.421(4), C-C_mean 1.399(1), C-H 1.123(2) Å, bond angles NCC 123.6(10)° and 117.2(7)°, and CNC 119.9(2)°. Torsion angles around C-N bonds are ?39° and ?45°. Phenyl groups are rotated by 48° from the position in which the C₃ axis lies in the phenyl ring plane.     

Structure of 1-Thia-closo-dodecaborane(11), 1-SB11H11, as determined by microwave spectroscopy complemented by quantum chemical calculations

The microwave spectrum of 1-thia-closo-dodecaborane(11), 1-SB(11)H(11), has been investigated in the 23-62 GHz spectral region. The molecule is found to have C(5v) symmetry. The spectra of several isotopomers have been assigned and a precise substitution structure of the non-hydrogen atoms has been determined. The structure is in quite good agreement with the one determined previously by electron diffraction. Density functional theory calculations at the B3LYP/cc-pVTZ level were found to predict a structure that is in good agreement with the substitution structure.     

Synthesis, microwave spectrum, and dipole moment of allenylisocyanide (H2C═C═CHNC), a compound of potential astrochemical interest

An improved synthesis of a compound of potential astrochemical interest, allenylisocyanide (H(2)C═C═CHNC), is reported together with its microwave spectrum, which has been investigated in the 8-120 GHz spectral range to facilitate a potential identification in interstellar space. The spectra of the ground vibrational state and of five vibrationally excited states belonging to three different vibrational modes have been assigned for the parent species. A total of 658 transitions with a maximum value of J = 71 were assigned for the ground state and accurate values obtained for the rotational and quartic centrifugal distortion constants. The spectra of five heavy-atom ((13)C and (15)N) isotopologues were also assigned. The dipole moment was determined to be μ(a) = 11.93(16) × 10(-30) C m, μ(b) = 4.393(44) × 10(-30) C m, and μ(tot) = 12.71(16) × 10(-30) C m. The spectroscopic work has been augmented by theoretical calculations at the CCSD/cc-pVTZ and B3LYP/cc-pVTZ levels of theory. The theoretical calculations are generally in good agreement with the experimental results.     

Conformation and intramolecular hydrogen bonding of 2-chloroacetamide as studied by microwave spectroscopy and quantum chemical calculations

The microwave spectrum of 2-chloroacetamide (ClCH2CONH2) has been investigated at room temperature in the 19-80 spectral range. Spectra of the 35ClCH2CONH2 and 37ClCH2CONH2 isotopomers of one conformer, which has a symmetry plane (Cs symmetry), were assigned. The amide group is planar, and an intramolecular hydrogen bond is formed between the chlorine atom and the nearest hydrogen atom of the amide group. The ground vibrational state, six vibrationally excited states of the torsional vibration about the CC bond, as well as the first excited state of the lowest bending mode were assigned for the 35ClCH2CONH2 isotopomer, whereas the ground vibrational state of 37ClCH2CONH2 was assigned. The CC torsional fundamental vibration has a frequency of 62(10) cm(-1), and the bending vibration has a frequency of 204(30) cm(-1). The rotational constants of the ground and of the six excited states of the CC torsion were fitted to the potential function Vz = 16.1( + 2.3) cm(-1), where z is a dimensionless parameter. This function indicates that the equilibrium conformation has Cs symmetry. Rough values of the chlorine nuclear quadrupole coupling constants were derived as chi(aa) = -47.62(52) and chi(bb) = 8.22(66) MHz for the 35Cl nucleus and chi(aa) = -34.6(10) and chi(bb) = 6.2(11) MHz for the 37Cl nucleus. Ab initio and density functional theory quantum chemical calculations have been performed at several levels of theory to evaluate the equilibrium geometry of this compound. The density functional theory calculations at the B3LYP/6-311++G(3df,2pd) and B3LYP/cc-pVTZ levels of theory as well as ab initio calculations at the MP2(F)/cc-pVTZ level predict correct lowest-energy conformation for the molecule, whereas the ab initio calculations at the QCISD(FC)/6-311G(d) and MP2(F)/6-311++G(d,p) levels predict an incorrect equilibrium conformation.     

Molecular structure of diphenylchlorophosphine in the gas phase

The molecular structure of diphenylchlorophosphine was determined by gas-phase electron diffraction in combination with quantum-chemical calculations. The molecule has the C ₁ symmetry with the following torsion angles around the P-C bonds: 140.2(3.1)° (C²P¹C⁸C⁹) and ?95.8(3.1)° (C⁸P¹C²C³). The ClPC² and ClPC⁸ bond angles are 101.9(4)° and 99.7°, respectively; the CPC bond angle is 103.1(1.3)°. The results of structural analysis agree with theoretical calculations of the geometry by the B3LYP/6-31G* and HF/6-31G* methods. The molecular geometries of some amines (fluoro-and chlorodiphenylamines) were calculated for comparison.     

Molecular structure of chloro-dodecafluorosubphthalocyanato boron(III) by gas-phase electron diffraction and quantum chemical calculations

The molecular structure of the chloro-dodecafluorosubphthalocyaninato boron(III) (F-SubPc) was determined with use of Gas Electron Diffraction (GED) and high-level quantum chemical calculations. The present results show that the F-SubPc molecule has a cone-shaped configuration, isoindole units are not planar, and the pyrrole ring has an envelope conformation. The structure parameters in the gas phase are determined. Some structural details can be observed such as the dihedral angle about the bond connecting the pyrrole ring and the benzene ring being ca. 174 degrees . High-level theoretical calculations with several extended basis sets for this molecule have been carried out. The calculations are in very good agreement with experimental methods: X-ray and GED. Nevertheless, some disagreements particularly related to the B-Cl bond distance found in GED are discussed. Vibrational frequencies were computed obtaining eight values below 100 cm-1 and three bending potentials were examined. They suggest that this molecule is very flexible.     

High precision delta(17)O isotope measurements of oxygen from silicates and other oxides: method and applications

The use of infrared laser-assisted fluorination to release oxygen from milligram quantities of silicates or other oxide mineral grains is a well-established technique. However, relatively few studies have reported the optimisation of this procedure for oxygen-17 isotope measurements. We describe here details of an analytical system using infrared (10 μm) laser-assisted fluorination, in conjunction with a dual inlet mass spectrometer of high resolving power ( approximately 250) to provide (17)O and (18)O oxygen isotope measurements from 0.5-2 mg of silicates or other oxide mineral grains. Respective precisions (1) of typically 0.08 and 0.04 per thousand are obtained for the complete analytical procedure. Departures from the mass-dependent oxygen isotope fractionation line are quantified by Delta(17)O; our precision (1) of such measurements on individual samples is shown to be +/-0.024 per thousand. In turn, this permits the offset between parallel, mass-dependent fractionation lines to be characterised to substantially greater precision than has been possible hitherto. Application of this system to investigate the (17)O versus (18)O relationship for numerous terrestrial whole-rock and mineral samples, of diverse geological origins and age, indicates that the complete data set may be described by a single, mass-dependent fractionation line of slope 0.5244+/- 0.00038 (standard error). Copyright 1999 John Wiley & Sons, Ltd.