Intermolecular hydrogen bonds, rotational spectrum, and structure of van der Waals complexes of (CH3)2O?CF2CH2 and (CH3)2O?CF2CHF

The results of molecular beam Fourier transform microwave (FTMW) investigations of the van der Waals complexes of dimethyl ether with 1,1-difluoroethene/trifluoroethene are reported. The rotational parameters of the complexes have been interpreted in terms of a C_s geometry with the two methyl groups lying out of the σ_v symmetry plane of complexes. The complexes are bound with three hydrogen bonds of which one is the stronger O?HC type and two are the weaker F?HC types. Some additional information on the structure and the hydrogen bond has been obtained from ab initio calculations.     

Triply hydrogen bonded van der Waals complexes: CH2F2?CF2CH2 and CH2F2?CF2CHF

The results of molecular beam Fourier transform microwave (FTMW) investigations of the van der Waals complexes of difluoromethane with 1,1-difluoroethene (DFE) and trifluoroethene (TFE) are reported. The rotational parameters of the complexes have been interpreted in terms of a C_s geometry with the two H or F atoms of CH₂F₂ lying out of the σ_v symmetry plane of the complexes. The complexes are bound by three hydrogen bonds, of which one is the stronger C-F?H-C type, and two are the weaker C-H?F?H-C or C-F?H?F-C types for DFM-DFE or DFM-TFE, respectively. The most notable difference in the two complexes is that the out of plane atoms are two hydrogens for DFM-DFE, but are two fluorines for DFM-TFE. Additional information on the structure and hydrogen bonding has been obtained from ab initio calculations.     

克里奇中间体CH2OO与CF3CF=CF2反应的动力学研究

本文使用OH激光诱导荧光方法研究了结构最简单的克里奇中间体CH₂OO和CF₃CF=CF₂的反应动力学. 在压强为10 Torr条件下,测量了温度在283,298,308和318 K的反应速率常数,分别为(1.45±0.14)×10^-13,(1.18±0.11)×10^-13,(1.11±0.08)×10^-13和(1.04±0.08)×10^-13 cm³·molecule^-1·s^-1. 根据阿伦尼乌斯方程,获得该反应的活化能为(-1.66±0.21) kcal/mol. 在6.3∽70 torr压力范围内,未观察到该反应的速率常数存在压力相关.     

ArF laser-induced discharge interruption in a mixture of C2H3Cl/CF4/CH4, CF4/CH4, and C2H3Cl/He

The ArF-laser (193-nm)-induced discharge interruption is comparatively described in a mixture of C₂H₃Cl/CF ₄/CH₄, CF₄/CH₄, and C₂ H₃Cl/He using a hollow-cathode-type discharge tube. The unfocused ArF laser (typically 27 mJ/cm² and 10 ns duration) illuminated both the negative glow inside the hollow cathode and the column between the two electrodes. With a 1.8-torr mixture of C₂ H₃Cl/CF₄, the discharge current of 1 mA was decreased rapidly with a current-decay time constant of 1 μs and a current-decay rate of 1 kA/s. With a 1.5-torr mixture of CF₄/CH₄, 2.2 μs and 450 A/s were obtained. With a 1.5-torr mixture of CH₂H₃Cl/He, a time constant of over 3 μs and a rate of less than 300 A/s were obtained. An analysis of the discharge interruption induced by ArF-laser irradiation is given in terms of photon-plasma kinetics. The current peak induced by ArF irradiation is also explained for a mixture of C₂H₃ Cl/He in terms of photoionization and photodetachment processes     

A theoretical study of the vertical ionization potentials of HNO,FNO, O3, CF2 and N2H2

The vertical ionization potentials of HNO, FNO, O₃, CF₂ and N₂H₂ have been calculated using Rayleigh—Schrodinger Perturbation Theory     

A study on the GVFF of CHF3, CH2F2, and CH3F

The complete GVFF of CHF₃, CH₂F₂, and CH₃F has been calculated from self-consistent-field ab initio energies, using a 4–31 G basis set. The larger part of the interaction force constants is close to those of the best available force fields from experimental data. Only one interaction term in CH₃F and the interaction force constants of the A₁ species in CH₂F₂ differ appreciably from the experimental ones. Using constraints from the ab initio studies we have improved the GVFF of CH₃F and CH₂F₂. It is shown that all comparable stretch-stretch interaction terms are of the same order of magnitude in the three molecules. The sign of all stretch/bend force constants are in accordance with those predicted by the hybrid orbital force field.     

Absolute Raman intensities of CH4, CH3D,CH2D2, CHD3, and CD4

Measurements of the absolute vibrational Raman intensities and depolarization ratios for the fundamental and some overtone and combination bands of CH₄, CH₃D, CH₂D₂, CHD₃, and CD₄ are reported. Experimental aspects of these measurements are discussed. The experimental data conform satisfactorily to all isotope intensity sum rules. The measured intensities and depolarization ratios, together with the vibrational potential function for CH₄, make possible the calculation of the four independent parameters of the isotopic invariant quantities $\text{α}{}^{\mathrm{S}}\text{= |}\text{?α}\text{?S}\text{|}$. The results deduced from these agree with all 36 experimentally observed values. Values of electro-optical parameters for the CH bond are calculated and discussed.     

Ab initio SCF investigation of the core and inner valence electron binding and relaxation energies of the CH4, C2 H2 and C2 H6 molecules

Ab initio ΔSCF values of the electron binding and relaxation energies are presented for the four deepest molecular orbitals of methane, acetylene and the two symmetry forms of ethane. Special attention is paid to the inner valence molecular region with regard to the symmetry-constrained Hartree—Fock calculations. The symmetry-constrained effect for the 1t₂ outer valence orbital of methane has also been investigated. The phenomena due to the broken symmetry are discussed on the basis of the configuration-interaction procedure.     

K-shell excitation of CH4, NH3, H2O,CH3OH,CH3OCH3 and CH3NH2 by 2.5 keV electron impact

The regions around the respective carbon, nitrogen and oxygen K-edges of CH₄, NH₃, H₂O, CH₃OH, CH₃OCH₃ and CH₃NH₂ have been investigated by electron energy loss spectroscopy using a beam of 2.5 keV electrons. All spectra show a number of discrete peaks just below the K-shell ionization threshold. These discrete structures have been interpreted as being associated with the promotion of a K-shell electron to Rydberg orbitals which converge to the K-shell ionization threshold.     

A theoretical investigation of the binding of TiCln to MgCl2

The structure of the (0 0 0 1) surface of the -MgCl₂ crystal has been investigated using DFT-GGA periodic calculations. The calculated surface relaxation is in agreement with LEED measurements. Motivated for the use of MgCl₂ as support for the Ziegler–Natta reaction, we have studied the adsorption of the catalyst (titanium chlorides as monomers or dimers) on the (1 0 0) and (1 1 0) MgCl₂ surfaces. The structures of adsorbed species are close to those previously found on cluster models: bridging chlorine atoms connect the Ti to the Mg atoms and the systems remain in high spin states. The (0 0 0 1) surface is the most stable face of the -MgCl₂ crystal; however it is Cl-terminated and henceforth poorly reactive; it had been suggested to deposit metallic Mg in order to improve its reactivity. Our modelling explains the failure of this tentative; the interaction between the deposited metal and the surface is repulsive and uncharged Mg atom does not bind.     

Experimental and theoretical investigations into the electronic structure of CF2Br2 by electron momentum spectroscopy

The binding energy spectra and electron momentum density distributions for the valence orbitals of CF₂Br₂ have been obtained by using electron momentum spectroscopy (EMS) at an impact energy of 1200 eV plus binding energy. The measured electron momentum profiles are compared with Hartree–Fock (HF) and density functional theory (DFT) calculations with different-sized basis sets. In general, the DFT-B3LYP calculation using the large basis sets of 6-311++G** and aug-cc-pVTZ fairly describe the experimental results. Moreover, the controversial orderings of the outer valence orbitals have been reassigned. The pole strength of the main ionization transition from the inner valence orbital of 1b₂ is determined.     

Investigation for long wavelength fir laser lines for EPR studies: New lines from CH2=CF2

The results described in this work are part of a systematic search for long wavelength laser lines to be used in high magnetic field EPR applications and in plasma diagnostic. Four new far-infrared laser lines of CH₂ = CF₂ (1,1 difluoroethylene), optically pumped by a waveguide CO₂ laser, have been discovered and characterized in wavelength, polarization relative to the pumping radiation and offset relative to the CO₂ center frequency. New measurements of polarization and offset of 5 already known laser lines are also reported. A table of all of the known CO₂ pumped FIR laser lines from this molecule is given.     

Infrared-microwave double resonance as an aid in assignment of optically pumped submillimetre laser lines: CH2CF2, CH2F2, and CH3OH

Infrared-microwave double resonance has been used to confirm recent assignments of optically pumped submillimeter wave laser lines in CH₂CF₂ and CH₃OH, as well as a tentative assignment of a line in CF₂H₂. Intracavity double resonance signals have also been obtained in CF₂CH₂ using a circular copper waveguide laser.     

Pionic x-ray intensities from C,CH2 and CD2

The relative intensities of the carbon L_α and L_β pionic X-ray lines from graphite, polythylene, and deuterated polyethylene have been measured. No differences between CH₂ and CD₂ were observed, but differences were found between graphite and the two polyethylene targets.     

A Theoretical Study of ãA2 CH2

The potential energy surface and dipole moment surfaces of the ã⁴A₂ electronic state of CH₂⁺ are calculated ab initio using an augmented correlation-consistent polarized valence quadruple-ζ (aug-cc-pVQZ) basis set, with the incorporation of dynamical correlation using the coupled cluster method with single and double excitations and perturbatively connected triple excitations [CCSD(T)]. We use these surfaces in the MORBID program system to calculate rotation and rotation-vibration term values for ã-state CH₂⁺, CD⁺₂, and CHD⁺ and to simulate the rotation and rotation-vibration absorption spectrum of CH₂⁺ in the ã⁴A₂ electronic state. Our work is motivated by studies of CH₂⁺ that use the Coulomb explosion imaging technique and by the goal of predicting spectra that may be obtained from discharge sources. Although the ã state is the lowest-lying excited state above the X?/Ã ground state pair, it turns out to be relatively high-lying, and we determine that T_e(ã)=30447.5 cm⁻¹. The equilibrium bond angle for ã-state CH₂⁺ is only 77.1°; as a result the asymmetric top κ value is close to 0, and the molecule is equally far from the oblate and prolate symmetric top limits in this electronic state.     

Single orbital relaxations accompanying core ionization in the isoelectronic series CH4, NH3, H2O,HF and Ne

Single orbital contributions to the total relaxation energy accompanying core ionization are computed by means of non-empirical LCAO MO SCF calculations within the ΔSCF formalism for the isoelectronic series CH₄, NH₃, H₂O, HF and Ne. Individual contributions to the total relaxation energy associated with the valence levels of essentially core-like 2s character are also presented.     

Elucidating surface properties of dry-etched ZnO using H2/CH4 and H2/CH4/Ar plasma

This paper reports a study of reactive ion etching (RIE) of n-ZnO in H₂/CH₄ and H₂/CH₄/Ar gas mixtures. Variables in the experiment were gas flow ratios, radio-frequency (rf) plasma power, and total pressure. Structural and electrical parameters of the etched surfaces and films were determined. Both the highest surface roughness and highest etching rate of ZnO films were obtained with a maximum rf power of 300 W, but at different gas flow ratios and working pressures. These results were expected because increasing the rf power increased the bond-breaking efficiency of ZnO. The highest degree of surface roughness was a result of pure physical etching by H₂ gas without mixed CH₄ gas. The highest etching rate was obtained from physical etching of H₂/Ar species associated with chemical reaction of CH₄ species. Additionally, the H₂/CH₄/Ar plasma treatment drastically decreased the specific contact and sheet resistance of the ZnO films. These results indicated that etching the ZnO film had roughened the surface and reduced its resistivity to ohmic contact, supporting the application of a roughened transparent contact layer (TCL) in light-emitting diodes (LEDs).     

Carbon molecular sieves from PET for separations involving CH4, CO2, O2 and N2

Carbon molecular sieves (CMS) have been made for the first time from PET textile fibres by carbonisation and pore mouth narrowing using CVD of benzene. The diffusion of O₂, N₂, CO₂ and CH₄ in these materials, and also in the commercial CMS Takeda 3A, was studied. It was found that the best PET based CMS was obtained after 10 min CVD time and had adsorption capacities and rates of diffusion similar to those of the Takeda 3A.     

Photoelectron and electronic absorption spectra of SCl2, S2Cl2, S2Br2 and (CH3)2S2

Photoelectron and electronic absorption spectra of SCl₂, S₂Cl₂, S₂Br₂, and (CH₃)₂S₂ have been measured and analyzed. Quantum chemical calculations (CNDO/ 2 and MWH (Mulliken-Wolfsberg-Helmholtz) have been carried out and the electronic structures have been described in terms of molecular orbital theory. The variation in differential photoionization cross-section as a function of incident photon energy and results of MO computations are used to identify ionization bands and assign ground state MO configurations. Suggested ground state electronic structures coupled with computed virtual MO's are used to interpret the visible and near-ultraviolet electronic absorption spectra. The low energy excited states are described as molecular states followed by the initial members of Rydberg series. Calculated oscillator strengths for molecular transitions are in good agreement with those observed experimentally. Quantum defects, δ, for the Rydberg states have been calculated from the Rydberg equation using the adiabatic first ionization potential.     

Differential cross sections of elastic electron scattering from CH4. CF4 and SF6 in the energy range l00-700eV

We investigate the differential cross sections （DCS） of elastic electron scattering from CH4, CF4 and SF6 at six impact energies in a range of 100 700eV by employing the independent atom model （IAM） together with the relativistic partial waves. The atom is present in an optical potential which is complex, spherically symmetric, and energy dependent. The optical potential of the atom is the sum of the direct static, dynamic polarization, local exchange and modified absorption potentials. The results obtained by using a modified absorption potential show significant improvements on the unmodified absorption potential results. The present results are generally in good agreement with experimental data available. In addition, the present results indicate that the structure of molecule manifests the observable effects on electron- molecule scattering.[第一段]