G. M. Begun

Vibrational Spectra and Valence Force Constants of the Square‐Pyramidal Molecules—XeOF4, IF5, BrF5, and ClF5

The infrared and Raman spectra of XeOF4, IF5, BrF5, and ClF5 have been recorded. The data have been tabulated and assignments of the fundamental vibration and combination frequencies made on the basis of a square‐pyramidal structure for these molecules. Valence force constants, based on estimated molecular parameters, have been calculated for these molecules. Comparisons between the different members of the series show that the bonding in XeOF4 is remarkably similar to that in the interhalogen compounds.

Vibrational spectra ot aqueous oxalate ion

New experimental data on the infrared and Raman spectra of aqueous oxalate ion are presented. The data are consistent with a staggered (D/sub 2d/) configuration for the ion. The fundamental vibrational frequencies (cm/sup -1/) assigned on this basis are: A/sub 1/- 1486, 900, 449; B/sub 2/-- 1579, 524; and E- - 1310, 761, 301. (auth)

Electron impact ionization studies of ferrocene, cobaltocene, nickelocene, and magnesocene

Negative and positive ions of ferrocene, cobaltocene, nickelocene, and magnesocene produced by collisions with monoenergetic electrons have been studied. Appearance potentials relative to the ionization potential of krypton have been determined for the products (C10H10M)+, (C5H5M)+, and M+. The ionization potentials derived from the present electron impact studies are in good agreement with recent photoelectron values. In all cases cyclopentadienyl anions were produced at low electron energies; however, their cross sections for formation differed by orders of magnitude. The most striking feature of the negative ion studies was the observation of a long‐lived parent negative ion of nickelocene at thermal electron energies, and a second broader compound negative ion resonance at approximately 1 eV. The autodetachment lifetime for the second resonance decreases from 60 μsec at 0.5 eV to 20 μsec at 1.5 eV. Cobaltocene also exhibits two long‐lived negative ion states in the energy region below one electron vol...

Infrared and Raman spectra of the boron trifluoride-dimethyl ether complex

Abstract The infrared spectra of liquid B10F3·(CH32O, B11F3·(CH3)2O, B10F3·(CD3)2O, and B11 F3·(CD3)2O have been observed in the region 300 cm−1 to 4000 cm−1. The Raman spectra of these compounds have also been examined. Assignment of the observed bands has been made which is consistent with the structure of the molecule and the isotopic data.

Infrared Spectra of the Isotopic Nitrous Oxides

The infrared spectra of N14N15O16, N15N14O16, and N15N15O16 have been observed from 2.5 μ to 20 μ using a model 112 Perkin‐Elmer spectrometer. The frequencies of the three fundamental vibrational bands and fifteen overtone and combination bands have been tabulated and compared with the frequencies of N14N14O16. Using known anharmonic constants and isotopic relations, approximate zero‐order frequencies have been calculated for the isotopic molecules. A set of force constants for infinitesimal displacements have been computed for the set of molecules, and the partition function ratios for the various species calculated from the data.

Infrared and Raman Spectra and Valence Force Constants of Iodine Oxide Pentafluoride (IOF5)

The infrared and Raman spectra of IOF5 have been recorded. The data have been tabulated, and assignments made on the basis of an octahedral structure with a fourfold symmetry axis. Valence force constants have been calculated. The bond angles are close to 90°, and there is an indication that the equatorial I–F bond lengths are about the same as the axial I–F bond length.

Mass Spectra and Metastable Transitions in Isotopic Nitrous Oxides

The mass spectra of the four species N14N14O, N14N15O, N15N14O, and N15N15O have been recorded. The (NO)+ fragment produced was found to be formed by rearrangement, as well as by loss of the end nitrogen. The mass spectrum of each of the nitrous oxides contained ions corresponding to metastable transitions. These ions were shown to arise from both spontaneous and collision induced dissociation of the parent molecule ion (N2O)+. The electron impact dissociation of nitrous oxide is discussed.

Infrared and Raman vibrational spectra of chloryl fluoride (ClO2F)

Abstract The infrared spectrum of gaseous chloryl fluoride has been examined in detail from 300 to 4000 cm −1 . The chlorine and oxygen isotopic structures of many of the fundamental overtone and combination bands have been resolved. The Raman spectrum of liquid chloryl fluoride has been observed from 100 to 1500 cm −1 and polarization measurements recorded. All the fundamental frequencies of the molecule have been observed in both the infrared and Raman spectra. Valence force constants have been calculated which closely reproduce the observed fundamental frequencies and their isotopic shifts.

Partition Function Ratios for Molecules Containing Nitrogen Isotopes

Nitrogen isotopic partition function ratios have been calculated for the following molecules and ions: N2, N2O, NO, NOCl, NO2, NO2—, NO3—, and N2O4. All available isotopic and anharmonic data have been used, and values of Q15/Q14 are tabulated for temperatures at intervals from 100°K to 600°K. Isotopic equilibrium constants calculated from the partition function ratios are compared with those that have been observed experimentally.

Raman and Infrared Spectra of BF3 Complexes with Diethyl Ether and Tetrahydrofuran, and the Isotopic Exchange of these Complexes with BF3

The Raman and infrared spectra of BF3·diethyl ether and BF3·tetrahydrofuran have been recorded for both the B10 and B11 compounds. The spectra have been compared to that of BF3·dimethyl ether and tentative assignments of the skeletal vibrations have been made. The isotopic data have been used to calculate theoretical equilibrium constants for isotopic exchange between the complexes and BF3. The calculated values are slightly higher but compare quite well with published values of experimentally determined separation factors.