The microwave spectrum and centrifugal distortion constants of difluoroborane,HBF2

The microwave spectra of two isotopic species of the unstable molecule difluoroborane have been measured between 8 and 36 GHz. Transitions have been measured up to J = 56 and K_a = 9 for H¹⁰BF₂, and up to J = 66 and K_a = 11 for H¹¹BF₂. Improved values for the rotational constants, boron nuclear quadrupole coupling constants, and quartic and sextic centrifugal distortion constants have been evaluated for both species.     

Study of the electronic structure of M(CO)5Cl complexes (M = Mn, Re) using X-ray spectroscopy and density-functional theory

The electronic structure of M(CO)₅Cl metal complexes (M = Mn, Re) has been investigated by X-ray emission spectroscopy. The obtained X-ray emission C Kα, OKα, Cl Kβ₁, MnLα, and MnKβ₅ spectra for Mn(CO)₅Cl and ReLβ₅ spectra for Re(CO)₅Cl have been interpreted on the basis of the quantum-mechanical calculations by the method of density-functional theory, using the Gaussian-98 program. The investigation of Mn(CO)₅Cl and Re(CO)₅Cl showed similarity of the electronic structure of both complexes. Only small differences have been revealed in the energy structure and orbital occupancies of the atomic orbitals of the corresponding molecular orbitals; these differences are caused by the difference of the type of metal ions and the molecule geometry. On the basis of the performed quantum-mechanical calculations, theoretical X-ray emission spectra have been constructed, which reproduce well the characteristic features of the corresponding experimental spectra of M(CO)₅Cl metal complexes (M = Mn, Re).     

Infrared spectrum and dynamics of the hydrogen bonded dimer (HF)2

We present a brief survey of our investigations of the spectrum of (HF)₂ in the range from 20 to 15000 cm⁻¹. A detailed dicussion of the transition assigned tentatively to the K = 2 → 1 subband of the “torsional” vibration (out-of-plane bending) close to 430 cm⁻¹ is presented. We give a summary of the K-sublevels known to date for all tunneling-vibrational states which have been investigated so far.     

Reaction products from a discharge of N2 and H2S: The microwave spectrum of two conformers of sulfur diimide (HNSNH)

The rotational spectra of two conformations of sulfur diimide (HNSNH) are reported. The HNSNH species are produced in a low-pressure microwave discharge of N₂ and H₂S. The microwave spectrum of the normal isotopic form, HNSNH, and dideutro form, DNSND, of the cis,trans and cis,cis forms have been observed. The electric dipole moment components of both forms have been determined. The molecular structures were determined from the experimental rotational constants and from geometry optimized ab initio calculations with 4-31G Gaussian basis sets and CEP-31G basis sets including polarization. The experimentally and theoretically derived molecular properties are found to be in good agreement.     

Analysis of the Ni K-edge X-ray absorption near edge structure in Ni((C2H5O)2PS2)2

The Ni((C₂H₅O)₂PS₂)₂ complex has been investigated using the X-ray absorption near edge structure (XANES) analysis. Nickel K-edge XANES spectra of the complex have been measured and theoretical calculations of the spectra have been carried out using the finite difference method; the calculation of molecular potential has been carried out both in the full potential and in the muffin-tin approximation. The analysis of results obtained has shown that a good agreement between theoretical and experimental spectra in the low-energy region is achieved only in the case of full potential calculations (beyond the muffin-tin approximation for the potential shape).     

The microwave,Raman, far infrared,and NMR spectra and structure of methylchloroformate

The microwave spectra of six isotopic species of methylchloroformate, ClCO₂CH₃, have been recorded from 18.0 to 40.0 GHz. Structural parameters have been determined, and it is shown that the only stable conformer at ambient temperature is the s-trans. The Raman and far infrared spectra of the vapor are reported. Four cases of Fermi resonance have been observed in the Raman effect. Both the methyl and methoxy torsions have been observed in the far infrared, and the methyl barrier to internal rotation has been determined to be 1.15 kcal/mole (1.19 kcal/mole for the CD₃ rotor), which is in agreement with the 1.23 kcal/mole obtained from the microwave splitting method. It is shown from both the ¹³C and ¹H NMR spectra along with the far-infrared data that only one conformer exists, which is contrary to what was previously reported. The vibrational spectrum of the solid is also reported and discussed.     

Microwave spectra and centrifugal distortion constants of oxetane

The microwave spectra of oxetane (trimethylene oxide) and its three symmetrically deuterated isotopic species have been observed on a Hewlett-Packard microwave spectrometer from 26.5 to 40 GHz. For the parent species, the β-d₂ and the αα′-d₄ species, about 300 lines have been assigned for each molecule, and for the d₆ species more than 600 lines have been assigned. The assignments range from v = 0 to v = 5 in the puckering vibration; although they are mostly Q transitions, either 3 or 4 R transitions have been observed for each vibrational state.The spectra have been interpreted using an effective rotational hamiltonian for each vibrational state, including five quartic distortion constants according to Watson's formulation, and a variable number of sextic distortion constants; in general, the lines are fitted to about ± 10 kHz. The distortion constants show an anomalous zig-zag dependence on the puckering vibrational quantum number, similar to that first observed for the rotational constants by Gwinn and coworkers. This is interpreted according to a simple modification of the standard theory of centrifugal distortion, involving the double minimum potential function in the puckering coordinate.     

K-shell excitation spectra of CO,N2 and O2

Electron energy loss spectra of CO, N₂ and O₂ have been recorded in the regions of carbon, nitrogen and oxygen K-shell excitation and ionisation. These results are compared to previous energy loss, photoabsorption and theoretical studies of the same spectral regions. Several inconsistencies in the published spectra are clarified in the present work. Comparisons with recent calculations of the K-shell continua of these molecules are presented. Vibrational structure in the K → π * transitions of CO (C 1s) and N₂ (N 1s) has been resolved in high-resolution studies (< 0.1 eV FWHM) of these species.     

Vibrational spectra of M3PCr4O16 (M = K,NH4)

The infrared and Raman spectra of the two phosphochromates M₃PCr₄O₁₆ (M = K, NH₄) have been recorded and analysed. The spectra could be interpreted on the basis of the vibrations of Cr-O-P, O-P-O and CrO₃ groups. A large number of vibrational bands have been observed for each mode due to the existence of different Cr-O bond lengths. The anion is more distorted in potassium phosphochromate. The three ammonium groups are distinct.     

Microwave spectrum,barrier to internal methyl rotation,dipole moment,and partial structure of dimethylketene

From the microwave spectrum of dimethylketene which has been recorded from 8 to 37 GHz, the following rotational constants were derived: A = 8 267.832 ± 0.8, B = 3 884.101 ± 0.03, C = 2 728.826 + 0.03 MHz. The dipole moment is μ_a = 1.94 ± 0.01 D. Substitution coordinates for all methyl group atoms have been obtained by investigating the spectra of six isotopic species of the molecule. The potential barrier V₃ hindering internal rotation of the methyl tops has been fitted to the multiplet width of a number of high-J ground state ^aQ-transitions which were observed as triplets. V₃ is 2065 cal/mole, keeping fixed I_α = 3.132 amu Ų and angle (methyl-top to a-axis) = 58.94° as obtained from the partial substitution studies.     

The Rotational Spectra of H2CCSi and H2C4Si

The microwave rotational spectra of two singlet chains H₂CCSi and H₂C₄Si, have been observed in a pulsed supersonic molecular beam by Fourier transform microwave spectroscopy. Following detection of the singly substituted rare isotopic species and D₂CCSi, an experimental structure (r₀) has been determined to high accuracy for H₂CCSi by isotopic substitution. In addition, the rotational transitions of the ²⁹Si and the two ¹³C isotopic species of H₂CCSi exhibit nuclear spin-rotation hyperfine structure. The component of the spin-rotation tensor along the a-inertial axis is abnormally large for each of these isotopic species, especially for that with ²⁹Si, where the magnitude of C_aa is in excess of 700 kHz.     

Microwave spectra of deuterated arsines: Distortion moment transitions of AsD3, microwave spectra of AsH2D and AsHD2, and the structure of arsine

Microwave spectra of three deuterated arsines have been measured and analysed. For AsD₃ distortion moment transitions have been observed for the first time, in the form of the K = ±1 ← ∓2 cluster; their frequencies have been combined with those of previously observed “normal” transitions to give rotational, centrifugal distortion, and ⁷⁵As hyperfine constants. For AsH₂D and AsHD₂, the measurements have been extended considerably and now include for the first time R-branch transitions; similar spectroscopic constants have been evaluated. The data have been combined with earlier results for AsH₃ and with vibrational data in a harmonic force field analysis. Both ground state average (r_z) and equilbbrium (r_e) structures have been estimated.     

Internal hydrogen bond,torsional motion,and molecular properties of 2-methoxyethylamine by microwave spectroscopy: Methyl barrier to internal rotation for 2-methoxyethanol

The microwave spectra of four substituted isotopic species of 2-methoxyethylamine (NH₂, NHD, NDH, ND₂) have been assigned. The molecule is found to exist in a gauche form with an intramolecular hydrogen bond of the NH?O type. The four possible sets of the amino hydrogen r_s corrdinates give different H?H distances, probably because the -NH₂ group is involved in large amplitude vibrations and because of changes in the heavy atom positions arising from the deuteration of the hydrogen bond. For the most abundant species many vibrational states have been analyzed and assigned to the two possible CO torsions in the molecule. A value V₃ = 3150 ± 50 cal/mol was found for the methyl torsional barrier and V₁ = 9 ± 3 kcal/mol for the other CO torsional barrier. A third set of observed vibrational satellites is probably assignable to the CC torsion. The determination of the dipole moment and of the quadrupole coupling constants gave values which were not in good agreement with those predicted from nonhydrogen bonded molecules. In addition a value V₃ = 3100 ± 100 cal/mol was calculated for the CH₃ torsional barrier in the related 2-methoxyethanol, using previous experimental data (Canad. J. Chem.50, 1149–1156 (1972)).     

Revealing the Spin-Hamiltonian and Characteristic Parameters of Paramagnetic Centers in Cu2+-Doped Potassium Metabisulfite (K2S2O5) Single Crystal by Electron Paramagnetic Resonance Technique

The present study is mainly related to finding out spin-Hamiltonian parameters of Cu²⁺-doped potassium metabisulfite [K₂S₂O₅] single crystals using electron paramagnetic resonance (EPR) technique which has been applied in the temperature range from 297 to 113 K for single and powder crystals of the title compound. The existence of two complexes and two Cu²⁺ sites for each complex was concluded from the angular variation of the EPR spectra. Having constructed the g and the hyperfine tensors, the spin-Hamiltonian parameters have been obtained for these two complexes. Using these parameters, the covalency parameter (α ²), mixing coefficients (α and β) and Fermi contact term (K) have been calculated.     

Microwave spectrum of fluorodihydroxy borane,BF(OH)2

Fluorohydroxy borane, BF(OH)₂, has been identified in the hydrolysis of trifluoroborane by microwave spectroscopy. The rotational and centrifugal distortion constants have been determined for the normal and d₂ species. From these constants the molecular structure has been determined. This molecule does not have C₂ symmetry and the structural parameters are $\text{r}\text{(BO}{}_1\text{) = 1.360}\text{A}\text{?}$, $\text{r}\text{(BO}{}_2\text{) = 1.365}\text{A}\text{?}$, ∠FBO₁ = 118.2°, and ∠FBO₂ = 121.0°. The inertia defects establish the planarity of the molecule. The dipole moment of 1.818 ± 0.007 D has been obtained from the measurements of the Stark effects.     

Enhancement of shake-up structure in alkali-metal-ion exchanged forms of α-Zr(HPO4)2 by sputtering

Mg Kα ESCA spectra of several α-Zr(PO₄)₂M₂ compounds (M = Li⁺, Na⁺, K⁺, Cs⁺) have been obtained. Satellite structure is observed at ～7–8 eV from the main P 2s peak (corresponding to ～15–16 eV from the main Zr 3d_{$\text{5}\text{2}$} peak). The intensity of the satellite depends on the counter-ion intercalated. For a given counter-ion it is strongly increased by sputtering, the rate of increase being also dependent on the counter-ion. This observation is interpreted mainly in terms of electron-defect formation similar to that involved in the formation of colour centres by radiation damage, and subsequent charge-transfer shake-up of the trapped electrons to the electron-deficient phosphorus or Zr(IV) centres.     

Microwave spectrum,conformation, and quadrupole coupling constants of cyclopentyl chloride

The microwave spectra of the normal and two isotopic species of cyclopentyl chloride have been observed and analyzed. For the normal isotopic species the rotational constants (in MHz) are A = 4547.77 ± 0.01, B = 2290.22 ± 0.01, and C = 2073.34 ± 0.01. From the rotational constant data, it has been shown that the stable molecular conformation is the bent axial form. Quadrupole coupling constants have been measured for the ³⁵Cl nucleus, the values being (in MHz) χ_aa = ?23.70 ± 0.10, χ_bb = 32.33 ± 0.36, and χ_cc = ?8.63 ± 0.37. When transformed to the CCl bond axis system, the coupling constants confirm the axial structure. Extensive vibrational satellite structure, presumably arising from the pseudorotational ring mode with a fundamental frequency of 52 ± 5 cm^?1, has been observed and assigned. No spectral evidence has been observed for a second stable molecular conformer.     

Infrared,Raman, and microwave spectra of ethaneselenol and the determination of the barriers to internal rotation

The infrared, Raman, and microwave spectra of gaseous ethaneselenol have been investigated. The rotational constants for both the more stable gauche and for the trans conformers are reported for the Et⁷⁸SeH, Et⁷⁸SeD, Et⁸⁰SeH, and Et⁸⁰SeD isotopic species. A proposed structure has been derived from a least-squares analysis of the moments of inertia. Dipole moment components have been obtained from each conformer using second-order Stark effects. For the gauche conformer, they are μ_a = 1.42 ± 0.01, μ_c = 0.37 ± 0.03, and μ_total = 1.47 ± 0.01 D. For the trans isomer they are μ_a = 1.217 ± 0.002, μ_b = 0.850 ± 0.001, and μ_total = 1.485 ± 0.002 D. The methyl barrier to internal rotation was calculated using observed frequencies obtained from the infrared and Raman spectra; a value of 3.59 ± 0.01 kcal/mole was obtained. Asymmetric potential functions have been calculated for both the EtSeH and EtSeD isotopic species. For the light species the potential constants for internal rotation around the CSe bond are V₂ = ?96.4 ± 1, V₃ = 432 ± 4, and V₆ = ?20 ± 2 cm^?1. The difference between ground-state energy levels of the two conformers was found to be 66 cm^?1. A vibrational assignment based on infrared and Raman spectra of the gaseous phase is presented.     

Infrared-microwave two-photon spectra of the ν3 bands of 12CH3F and 13CH3F

Infrared-microwave two-photon spectra have been obtained for the ν₃ bands of ¹²CH₃F and ¹³CH₃F with a two-photon spectrometer employing a CO₂ laser and a computer-coupled microwave source operating in the 8–18 GHz region. Even though the intensities of the spectra for the double parity levels in these molecules are inversely proportional to the square of the microwave frequency, transitions have been observed with microwave frequencies of up to 16 GHz. Comparison of these observed two-photon frequencies to frequencies predicted from infrared laser Stark spectroscopy, and to frequencies calculated from vibration-rotation parameters obtained by fitting these and other frequencies, shows agreement to within a few MHz. Spectroscopic parameters for the ground and ν₃ excited states of the two species are reported.     

Structure of dichlorine monoxide as studied by microwave spectroscopy. Determination of equilibrium structure by a modified mass dependence method

The microwave spectra of four isotopic species of dichlorine monoxide (OCl₂) have been observed, and the rotational constants have been obtained. The r_m structure for each isotopic species has been determined by Watson's method. The equilibrium structure has been estimated by taking proper averages of r_m structures to be $\text{r}{}_{\mathrm{e}}\text{(OCl) = 1.69587(7)}\text{A}\text{?}$ and ∠_eClOCl = 110.886(6)°. The general applicability and the merit of the present method for estimating the equilibrium structure are pointed out.