Application of self-consistent-field ab initio calculations to organic molecules

The local symmetry force constants of propene have been calculated from extended (4–31 G) self-consistent-field ab initio energies. The previously developed scaling method was used to adjust seven scale factors on 84 observed frequencies of propene and deuterated analogues. The latter were taken from the literature. The average difference between observed and calculated frequencies amounted to 8·3 cm^-1 or 0·63 per cent. The stretching force constant of the carbon-carbon single bond was found to be 0·3–0·4 mdyn Å^-1 larger than those of ethane and propane. Force constants of the CH₃ groups in the series: ethane, propane, propene, methanol and dimethyl ether, written in local symmetry coordinates, seem to be transferable within about 2 per cent. Individual CH bond stretching force constants, written in internal coordinates, show significant chemical variations.     

A comparison of semi-local and non-local pseudo-potential techniques: calculations on Fe and FeH+

A new parameterization scheme is proposed for valence electron calculations which employ the pseudopotential formalism. This scheme has been implemented in calculations for Fe, Fe⁺, Fe²⁺, Fe³⁺ and FeH⁺. In comparison with conventional all-electron calculations the errors are of the order of 1 per cent in valence orbital energies, 0·5 per cent in ionization energies and 2 per cent in the molecular binding energy. Detailed comparisons are made between the present method, which is formulated in terms of orbital projection operators, and recent calculations based on local, angular momentum dependent, effective potentials. The two approaches are found to be capable of almost equal accuracy.     

Absolute cross sections for collision-induced depolarized scattering of light in krypton and xenon

Depolarized Raman spectra of binary collisional pairs of atoms in krypton and xenon are obtained at gas densities of 1–10 amagat. Absolute intensities relative to a known rotational transition of nitrogen are determined. For light of 4880 Å wavelength incident in the x-direction, polarized in the z-direction and scattered in the y-direction of a cartesian frame x, y, z, at a frequency shift of -12 cm^-1, the differential scattering cross section per unit wavenumber band times volume, is found to be 1·10 × 10^-52 cm⁶ ± 10 per cent for krypton, and 4·76 × 10^-52 cm⁶ ± 10 per cent for xenon, if the sum of both polarizations is considered. Wave-mechanical and classical computations reproduce both the shape and the intensity of the experimental spectra if the so-called point-dipole model of the anisotropy of the polarizability of collisional pairs of atoms is used. Other models of the anisotropy are seen to be overcorrected by these criteria.     

Microwave cyclotron resonance of hot electrons in p-type GaSb

A microwave photocreated cyclotron resonance signal is observed in p-type GaSb in the temperature range 1–30 K. Circular polarization and other measurements identify the carriers as electrons in the (000) conduction band. The problem of a surface effect on the measured peak position, reported for the first time is avoided by bulk carrier creation. An exponential loss of signal intensity at 27 K is explained by the theory of background plasma effects. The measured ωτ of 1·5–4 yields an electron collision time of τ ～ 10^?11 sec. The scattering mechanism at liquid helium temperatures is identified as being partly due to neutral defect acceptor scattering of hot electrons, with an unidentified residual scattering process. The electron polaron effective mass is measured to be (m *(polaron)/m₀) = 0·0412 ± 0·0012 for hot electrons with an average energy of ～ 14 MeV and is isotropic within 1 per cent. When corrections for conduction-band non-parabolicity and hot polaron effects are applied, the band-edge free electron mass is calculated to be (m₀*(free)/m₀) = 0·0396 ± 0·0021 (±5·2 per cent).     

Electronic polarisabilities of ions in alkali halide crystals

Tessman, Kahn and Shockley calculated the electronic polarisabilities of ions in alkali halide crystals using the long wavelength limiting values of the visible light dielectric constants. We have recalculated these widely used polarisabilities using the more accurate room-temperature dielectric constant data of Lowndes and Martin and a better minimisation procedure of Pirenne and Kartheuser. We have also calculated for the first time the low temperature values of these polarisabilities. The computed values of the polarisability in ų are Li⁺ 0·029, Na⁺ 0·285, K⁺ 1·149, Rb⁺ 1·707, Cs⁺ 2·789, F^? 0·876, Cl^? 3·005, Br^? 4·168, I^? 6·294 at 300°K and Li⁺ 0·029, Na⁺ 0·290, K⁺ 1·133, Rb⁺ 1·679, Cs⁺ 2·743, F^? 0·858, Cl^? 2·947, Br^? 4·091, I^? 6·116 at 4°K. The relative standard deviations for all the alkali halides are 1·20 and 1·43 per cent at 300°K and 4°K respectively justifying the additive nature of the individual ion polarisabilities.     

Theoretical study of the O(1D) + H2(1Σ g +) reactive quenching process

Classical trajectory calculations have been made for the system O(¹ D) + H ₂(¹Σ _g ⁺) →OH(²Π) + H(² S) using an analytical singlet ground state surface for H ₂O. A rate constant of 1·73 × 10^-10 cm³ molecule^-1s^-1 at 300 K has been obtained. The distribution of energy in the products is approximately 30 per cent in translation, 45 per cent in vibration and 25 per cent in rotation. Because of the preponderance of vibrationally long-lived trajectories, statistical theories gave a good interpretation of the gross features of the reaction.     

Shock-wave compression of x-cut quartz as determined by electrical response measurements

The mechanical response of x-cut quartz in the vicinity of the Hugoniot elastic limit is determined from measurements of the piezoelectric current from samples impact loaded from 26 to 130 kbar. The Hugoniot elastic limit is determined to be 60_?1·5⁺³ kbar at a compression of 0·066_?0·002^+0·004 This Hugoniot elastic limit corresponds to a shear strength of 5·5 per cent of the C₄₄ shear modulus. For stresses well above the Hugoniot elastic limit the electrical current measurements show that the material exhibits a substantial reduction of shear strength. The pressure derivative of the bulk modulus is determined to be 4·5, substantially less than the ultrasonic value. The experimental records show evidence for a time delay for reduction of shear strength which varies from about 10^?7 sec immediately above the 60 kbar Hugoniot elastic limit to about 10^?8 sec for stresses well above the Hugoniot elastic limit. The measurements also show stress relaxation below the Hugoniot elastic limit between 40 and 60 kbar.     

EID study on the system platinum-hydrogen

Electron induced desorption of hydrogen on polycrystalline platinum has been studied in continuation of former work. The results remain consistent with a supposed adsorption model implying that electron induced H⁺ emission is restricted to hydrogen adsorbed only at particular sites occupying not more than 1 per cent coverage. These sites are ascribed to characteristic and stable surface impurities which are not influenced by the improved target treatment applied. Depletion of sites by sputter cleaning is cancelled by recovery during annealing. The highest observed H⁺ yield (all available sites filled with hydrogen) is 2 · 10⁻⁵ ions per electron. The total cross section for desorption by electron impact is 2 · 10⁻¹⁷ cm². Complex interaction phenomena between the electrons and the hydrogen covered platinum surface have been observed.     

Electron spin resonance investigation of carbon-13 hyperfine interactions in nitrobenzene anion radical

Synthesis of carbon-13 enriched nitrobenzene which contains 22·5 mole per cent of nitrobenzene-1-¹³C and an equal amount of nitrobenzene-4-¹³C has been accomplished. We report the carbon-13 hyperfine interactions in the corresponding anion radicals in a variety of solvent media. In hexamethylphosphoramide a _C1 = -7·05 gauss and a _C4 = 6·14 gauss. These couplings change to -9·03 gauss and 5·31 gauss, respectively, when the solvent medium is dimethylformamide containing 0·598 mole fraction of water. The solvent dependence of a _C1 is consistent with the radical remaining planar as opposed to adopting a pyramidal conformation at the nitrogen when hydrogen bonds form between the radical anion and protic solvents. Data reported here provide an experimental means to estimate the spin density distribution in nitrobenzene anion.     

Number of 59·5 keV-photons per decay of241Am

Number of 59·5 keV-photons per decay of²⁴¹Am equal to 0·355±0·003 was determined from activity and gamma-emission rate measurements.     

Measurements of gf-values for FeI lines

Iron atoms were formed in an all-glass shock tube from mixtures of Fe(CO)₅ in Ar. Observations of the reflected shock region have led to the following gf-values (within ±20 per cent) for selected low-excitation lines of multiplet 13: 1·05 × 10^-4 for the line at 6280·620 A, 1·70 × 10^-4 at 6358·690 A, and 6·70 × 10^-5 at 6498·950 A. The following results (within ±30 per cent) were obtained for gf-values of high-excitation lines belonging to multiplets 1032, 843 and 928, respectively: 1·05 × 10^-1 for the line at 5187·92 A, 3·00 × 10^-1 at 5242·50 A, and 1·10 × 10^-1 at 5379·58 A. The new measurements correspond to an increase of the more recently accepted f-number scale by about a factor of two.Curves of growth for the strong, high-excitation lines have been used to determine half-widths for collision broadening of Fe by the gas mixture existing under equilibrium conditions. The most frequent collision partners are argon atoms and electrons. At room temperature, the broadening coefficient is 0·15 cm^-1 at 1 atm, which is about five times larger than the values normally observed in nonreactive collisions, but is appreciably smaller than the line-widths expected for hydrogen-atom broadening of iron lines.Particular care was exercised in these investigations in order to define the gas composition in the reflected-shock region. Large systematic errors were encountered when a conventional static mixing procedure was used in place of a dynamic procedure, which is required for adequate composition control of strongly-adsorbed gases [Fe(CO)₅] in a large excess of inert diluent (Ar). The consistency of our observations was demonstrated by showing that, although measured intensity-time data were strongly affected, final estimates for gf-values were not influenced by the following systematic variations in experimental technique: changes in the mole ratio of Fe(CO)₅ to Ar produced by temperature alterations in the liquid Fe(CO)₅-bath which served as an equilibrium source for Fe(CO)₅; changes in the flow rate of Ar through the isothermal Fe(CO)₅ supply source; changes in the volume of the liquid Fe(CO)₅ supply source; admixture of excess CO to the Ar which served as carrier gas for Fe(CO)₅; changes in the slit functions; changes in the concentration of the dominant collision partners for the iron atoms.     

Predictions of climate changes caused by man-made emissions of greenhouse gases: A critical assessment

Predictions of the most advanced computer models of the changes in the global climate that may result from man-made emissions of greenhouse gases are described and assessed in the light of the uncertainties in future emissions and atmospheric concentrations of these gases, and of the limitations of the models

Predictions of the globally averaged temperature rise, produced by the doubling of atmospheric carbon dioxide over 70 years, range from 1·3 to 2·6°C, on average about 0·3°C decade^?1. The scattering of solar radiation by atmospheric aerosols is calculated to reduce this global warming to about 1·0°C or 0·2°C decade^?1. Warming is predicted to occur everywhere but to be most marked in high latitudes of the Northern Hemisphere.

Globally averaged precipitation is predicted to rise by a few per cent but with large geographical variations and areas of both increase and decrease. The largest increases are expected to occur in intertropical convergence zone, and in middle and high latitudes, especially in winter. Decreases are predicted in the subtropics. The best current estimate of the rise in sea level resulting from an annual increase of 1% p.a. of carbon dioxide is 4 cm decade^?1.     

Interatomic force constants studies of AMF3perovskite-type crystals (A = K,Rb; M = Mg,Ni, Co,Zn, Mn)

A simple model involving only three force constants allows us to evaluate the short range interactions in perovskite fluorides from the experimental values of the elastic constants and the lattice parameters of these compounds. The results indicate that the A-F bonds are quite central in character whereas the M-F bonds are axially symmetric; thus the short range A-F interactions are assumed to have the Born-Mayer form:ZZZZZBy studying the variations of the force constants with respect to the lattice parameter r, it is determined that ρ = 0·232 , λ = 2·8 × 10^?8 ergs for K⁺-F^?; ρ = 0·232 , λ = 4·1 × 10^?8 ergs for Rb⁺-F^?; λ₂, ρ₂ and ρ₂ are respectively 6·9 × 10^?10 ergs, 0·34 , 0·98for Co²⁺-F^? and 2·9 × 10^?10 ergs, 0·46 , 1·40for Mn²⁺-F^?. Taking into account both the short range repulsive potential and the long range electrostatic potential we can study the variations of the lattice energy as a function of r near the equilibrium position and deduce a theoretical value of the lattice distance. In spite of the simplicity of the model, the discrepancy between the experimental and the theoretical values is less than 10 per cent for all the compounds.     

Thermal conductivity of nitrogen in the temperature range 350–2500 K

The thermal conductivity of nitrogen is determined in a conductivity column instrument in the temperature range of 338 to 2518 K with an estimated uncertainty of about ± 1·5 per cent. The experimental data points are correlated by a cubic polynomial in temperature, viz. k(T)/(mW m^-1 K^-1) = 12·18 + 0·05224(T/K) - 0·6482 × 10^-6(T/K)² - 0·2765 × 10^-9(T/K)³. These conductivity values determined from heat transfer data taken in the continuum regime are found to be in fair agreement with the values obtained from similar data referring to low pressure range.

The present results are compared with the conductivity determinations of other workers and with the predictions of various theories developed for polyatomic gases. It is pointed out that a reliable calculation of thermal conductivity over an extended temperature range is impossible at the present time due to the absence of a large variety of experimental molecular data needed for such an effort. Average values of the vibrational energy diffusion coefficient, D _vib, are computed from the present k(T) data.     

Cyclotron resonance under uniaxial stress in tellurium

We present cyclotron resonance measurements in pure Te for B 6 c in the Voigt configuration under uniaxial stress p 6 c up to 2·10⁹ dyn/cm². The maximum shift of the resonance line of about 10 per cent is interpreted as change of the band structure. Shift and line shape are in good agreement with theoretical predictions.     

Differential elastic and quenching cross sections for Ar*(3P) and CO2(X1 ∑ g +)

The energy dependence of the differential scattering of metastable Ar*(³P) by ground-state CO₂(X¹ ∑ _g ⁺) has been studied at relative kinetic energies from 58 to 126 meV over an angular range of 5–160° c.m. using crossed molecular beams. The position and curvature of rainbow maxima, which are observed at each energy, are used to obtain parameters for a Lennard-Jones (12, 6) spherically symmetric potential. The position of the minimum, r _m = 5·02 ± 0·65 Å, is identical to that for K + CO₂ and the well depth, ε = 16·3 ± 0·8 meV, is about 10 per cent greater. The scattered intensity shows a distinct fall-off on the dark side of the rainbow compared to that expected for elastically scattered Ar*. This depletion, caused primarily by the quenching of Ar*, is analysed in terms of the optical-shadow model to determine the energy dependence of the observed quenching cross section, which is predicted to have a maximum of 67 Ų at 193 meV.     

Neutron diffraction determination of the number and displacement of the atoms in the diffuse ω-phase of Zr0·8Nb0·2

Alloys of Zr and Nb with Nb concentrations between 5 and 17 per cent undergo an athermal displacive transformation from b.c.c. to the hexagonal ω-phase. The ω start temperature depends on Nb concentration. The ω structure is derived from b.c.c. by the displacement of atom rows parallel to [111]. For Nb concentrations greater than ? 17 per cent the Bragg reflections characteristic of the ω-phase never develop under athermal conditions but a diffuse scattering in their vicinity is present. The alloy in this state is referred to as diffuse omega phase and omega domains cannot be imaged in the electron microscope. Coherence of the displaced atoms with the b.c.c. lattice allows the determination of the number of displaced atoms and their mean displacement from intensity measurements of the b.c.c. Bragg reflections. At 300°K some 32 per cent of the atoms in the Zr_0·8Nb_0·2 alloy are displaced 56·2 per cent of the way to the ideal ω positions as represented by the AlB₂ structure. Both the number of atoms and their mean displacement increase as the temperature is lowered. We believe these results are the first to quantify the diffuse omega phase.     

Electron spin resonance study of oxygen-17 enriched N,N-dimethyl-4-nitroaniline radical anion

N,N-Dimethyl-d₆-4-nitroaniline enriched to approximately 11 atom. per cent in oxygen-17 has been prepared and the oxygen-17 isotropic hyperfine interaction in the corresponding radical anion has been examined. In dry dimethylformamide solution we find a _O = -8·85 ± 0·02 and a _N = 11·39 ± 0·10 gauss, while in moist acetonitrile solution a _O = -8·82 ± 0·07 and a _N = 12·23 ± 0·11 gauss. These results substantiate the recent suggestion that the isotropic oxygen-17 splittings in π-radicals may be described by a single parameter equation analogous to McConnell's relation for aromatic proton splittings, i.e. a _O = Q _OρO ^π, where Q _O = -41 ± 3 gauss.     

Crystal field parameters and phase transitions in ErSb

The crystal field levels of the Er ($\text{J =}\text{15}\text{2}$) ion in a single crystal of ErSb have been measured by inelastic neutron scattering. The crystal field parameters obtained by a least squares fit to the spectra at several temperatures are: B₄ = (0·473 ± 0·005) × 10^?2°K and B₆ = (0·59 ± 0·06) × 10^?5°K, which differ considerably from the values o by interpolation from measurements on other compounds. In addition the temperature dependence of the magnetic scattering in the vicinity of the Néel temperature (T_N = 3·55°K) clearly demonstrates that the transition is second order in contrast to the first order behavior suggested by specific heat measurements. Also, any lattice distortion accompanying the magnetic ordering is less than 0.1 per cent, the resolution of the present experiment.     

Electronic properties of Bi2Se3 crystals

Bismuth selenide crystals were grown from melts with liquid concentrations within 0·2 per cent of stoichiometry. The resulting crystals were examined structurally showing that single crystal samples could be cut for electronic property measurements. Samples were n-type and degenerate (n ～ 2 × 10²⁵ m^?3). Hall, magnetoresistance and Shubnikov-de Haas measurements confirm that the carriers lie in a single minimum located at the centre of the Brillouin Zone. The results are discussed in terms of a non-ellipsoidal band model, and the degeneracy discussed in terms of a defect model.