Variational calculations of the static polarizability of H2 and of the dipole-dipole contribution to the dispersion energy between two hydrogen molecules

The convergence of variation-perturbation calculations using non-linear variation parameters has been examined for the static polarizability of H₂ and for the coefficient (C₆) of the R ^-6 term in the multipole expansion of the H₂-H₂ dispersion energy. Using a correlated ground state wavefunction, and one excited state for each of the parallel and perpendicular components of the polarizability, a single variational parameter for each state gave 96 per cent of the exact value of α_⊥ and 91 per cent of the exact value of α_‖. A second variational parameter for the parallel component gave 94 per cent of α_‖. The same procedure gave the spherical average and anisotropy of C₆ to an accuracy of about 90 per cent. By extending the calculations into the region where overlap of the orbitals of the two molecules becomes significant, it is shown for the end-on configuration that the C₆ R ^-6 term underestimates the dispersion energy near the van der Waals' minimum by roughly 10 per cent.     

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.     

Rotational band contour analysis in the Ã1A′-[Xtilde]1A′ electronic systems of substituted naphthalenes

The 0₀ ⁰ bands of the à ¹ A′-[Xtilde] ¹ A′ systems of 1-fluoro, 1-hydroxy and 1-aminonaphthalene have been investigated by rotational band contour analysis. The 0₀ ⁰ bands in 1-fluoro and 1-hydroxynaphthalene are 70 per cent type A and 30 per cent type B, and 75 per cent type A and 25 per cent type B hybrids respectively: the electronic transition moment vector has been rotated by about 15° towards the carbon atom C₃ by the F and OH substituents compared to naphthalene (in which, in the Ã-[Xtilde] system, it is along the long in-plane axis). In 1-aminonaphthalene it seems likely that the 0₀ ⁰ band is predominantly type A, but it could not be observed with sufficient intensity to be able to obtain the excited state rotational constants with any certainty.     

Electron spin resonance and structure of the CO- 2 radical ion

Analysis of the electron spin resonance spectrum shows that CO^? ₂ radical ions are trapped in sodium formate at room temperature after irradiation of the crystal with high energy γ-rays. This radical is bent with an angle of about 134° and has a ² A ₁ ground state. From the experimental values of the ¹³C coupling coefficients and the g values, coefficients are derived for the mixing of atomic orbitals in the half-filled 4a ₁ molecular orbital which appears to be 14 per cent carbon 2s, 66 per cent carbon 2p _z and 11 per cent of each oxygen 2p _z . There is also coupling to the sodium nucleus in an adjacent cation.     

Computation and analysis of the dynamic structure factor S(k, ω) for small wave vectors

Molecular dynamics (MD) calculations have been performed for the Lennard-Jones (12-6) potential function using 2048 particles. Using conventional parameters the results may be compared with those for liquid argon.

The dynamic structure factor S(k, ω) has been determined both by Fourier inversion of the intermediate scattering function F(k, t) and from the longitudinal current-current correlation function C _∥(k, t). Particular attention was paid to the recurrence time of the system. The results for S(k, ω) by the two methods agree within 5 per cent for the whole region of small k-vectors considered. Double Fourier inversion of the van Hove function G(r, t) led to insufficiently accurate results for these small k-values. In view of the present data, the MD-results of Levesque et al. [1] for S(k, ω) have only a qualitative character. These latter data appear to contain truncation errors due to incomplete Fourier transformations.

Using a hydrodynamic assumption for F(k, t) we were able to extract the transport coefficients, the velocity of sound and the ratio of the specific heats in the limit of large wave lengths or small k. The velocity of sound was obtained by exploiting the MD generated anomalous dispersion curve of sound waves. Anomalous dispersion was found to set in for kσ ～ 0·25. A sound speed of 880 ms^-1 has been determined which is in excellent agreement with experimental values for liquid argon. The total error for the MD value amounts to about 5 per cent. In contrast, the ratio of the specific heats γ and the transport coefficients D _T and Γ (thermal diffusivity and sound attenuation) were determinable only with an accuracy of 15 per cent due to the need for larger extrapolations. Nevertheless, we found D _T, Γ and γ in agreement with experimental values within 5-10 per cent.     

Evidence for an anisotropic contribution to 3 J FF from the 19F N.M.R. spectrum of hexafluorocyclopropane dissolved in a nematic phase

Analysis of the fluorine N.M.R. spectrum of a sample of hexafluorocyclopropane dissolved in p-ethoxybenzylidene-p-n-butylaniline (EBBA) has given the magnitudes and relative signs of three anisotropic and three isotropic coupling constants. The anisotropic couplings ² T _FF and ³ T _FF(cis) appear to be entirely dipolar in origin, whereas the value of ³ T _FF(trans) can be considered as 86 per cent dipolar, the remaining 14 per cent being attributed to an anisotropy in the electron-coupled spin-spin interaction.     

The effects of fast-neutron irradiation on tensile strengths of carbon fibers

Two types of commercially available carbon fibers (high tensile strength, HTS, and high modulus, HMS) were irradiated in the Ground Test Reactor in environments of air and of liquid nitrogen (LN₂). The tensile strength of HTS fibers irradiated in air increased sharply above a fast-neutron fluence of 6 × 10¹⁷ n/cm² (E> 1 MeV) and was 17 per cent greater than the strength of unirradiated control fibers at a fluence of 8.5 × 10¹⁷ n/cm², but then the strengrh began to decrease for additional neutron exposure in air and fell 25 per cent below the control strength at the highest fluence of 4.5 × 10¹⁸ n/cm². However, when irradiated in LN₂ where surface oxidation did not take place, the room-temperature strength of HTS fibers continued to increase beyond 8.5 × 10¹⁷ n/cm² and became almost 30 per cent greater than the control strength for a fluence of 3 × 10¹⁸ n/cm². The tensile strength of HMS fibers irradiated in air increased slowly but steadily with neutron exposure and was only 4 per cent greater than the control strength at the highest fluence of 4.5 × 10¹⁸ n/cm²; the room-temperature strength of the HMS fibers decreased by 13 per cent when irradiated to a fluence of 3 × 10¹⁸ n/cm² in LN₂.     

implantation of Bi into GaP. II. channeling studies

The channeling technique has been used to investigate the properties of Bi-implanted Gap. Measurements of the crystal disorder for 100 keV room temperature implants indicate a damage vs dose curve corresponding to ～13000 displacements/ion in the linear region and saturation at ～1.5 × 10¹³ Bi ions/cm². Annealing of the radiation damage has been observed and indicates two annealing steps at ～450°C for light damage and ～750°C for implants in the 1 × 10¹⁴/cm² range. Difficulties associated with the thermal decomposition of the implanted area have been overcome with the use of SiO _x coatings. The experimental details associated with the use of the SiO _x layer and with the use of a C¹² beam to obtain better depth and mass resolution in the backscattering spectrum are discussed. The lattice location measurements of the Bi impurity show ～50 per cent of the Bi atoms to be along the 〈110〉 string after a 900°C anneal for a 7.5 × 10¹³/cm² implant. In addition, the spectra show ～25 per cent of the Bi atoms have diffused to the surface. Correlations of these lattice location results with measurements of the photoluminescent intensity of the GaP (Bi) isoelectronic trap show an agreement in trend with anneal temperature but indicate a factor of ～10 more substitutional ions in the channeling measurement as compared to the photoluminescence results.     

Electron spin resonance detection of acrylic acid radical anions and related species in low temperature glasses

A contracted gaussian basis set in double-zeta form (plus polarization functions) has been used to calculate the vibrational characteristics of CH₃F by means of an ab-initio SCF finite-difference method. The diagonal force constants, with an error of about 10 per cent, are an upper limit to experiment. The off-diagonal interaction constants give a correct picture of the molecular force field, unlike the Hybrid Orbital Force Field model. With the derivatives of a dipole moment corresponding to a good theoretical evaluation (about 2D), it is possible to discuss the problem of signs in infra-red intensity analysis.     

Das Positronenspektrum von22Na und die Ruhemasse des Neutrinos aus dem β+-Zerfall

Theβ ⁺ spectrum of²²Na has been measured with the Heidelberg (π/2) √13 iron-freeβ-ray spectrometer. Particular attention was paid to the upper end of the continuum. The maximum energy was found to beE _max=(545.7 ±0.5) keV. The rest mass of the neutrino connected withβ ⁺ decay was found to be zero with an upper limit of 4.1 keV (67 per cent confidence).     

Substituent effects on the geometry of some trigonal radicals

A simple level of ab initio molecular orbital theory with a split-valence shell basis with d-type polarization functions (6–31G*) is used to predict equilibrium geometries for the ground and some low-lying excited states of AH_n molecules and cations where A is carbon, nitrogen, oxygen or fluorine. The results are shown to be close to the limit for single determinant wave functions in cases where corresponding computations with more extensive bases are available. Comparison with experimental results also shows good agreement although a systematic underestimation of bond lengths up to 3 per cent is evident. For systems where no experimental data are available, the results provide predictions of equilibrium geometry.     

Giant magnetoresistance in bulk samples of LaMnO3 with varying Mn4+ content

Magnetoresistance (MR) in bulk samples of LaMnO₃ has been investigated by varying the Mn⁴⁺ content from 10 to 33 per cent by chemical means, without aliovalent doping. With the increase in Mn⁴⁺ content, the structure of LaMnO₃ changes first from orthorhombic to rhombohedral and then to cubic and the material becomes increasingly ferromagnetic, exhibiting a resistivity maximum akin to an insulator-metal transition atT _Peak, just below the ferromagneticT _c. The magnitude of MR is highest in the cubic sample (with 33% Mn⁴⁺) around theT _Peak, and negligible in the non-magnetic orthorhombic sample (12% Mn⁴⁺).     

Relative thermoluminescence effects of alpha‐ and beta‐ radiation

Abstract

A study has been made of the relative thermoluminescence response to α- and β-radiation of six phosphors (two types of natural fluorite, CaF₂: Mn, CaF₂: Tb, CaSO₄: Mn and quartz) using samples which are thin compared to the range of the α-particles. The α- and β-radiations induce the same glow peaks, but at low doses (<100 rads) the TL response per rad of α-radiation (3.7 MeV) is less than that per rad of β-radiation in all the glow peaks studied. The α-efficiency ranges from 53 per cent for CaF₂: Mn to 2 per cent for quartz (110°C peak) at 3.7 MeV and decreases with decreasing α-particle energy. At higher doses (10⁶?10⁷ rads) the TL responses to α- and β-radiation become equal within 15 per cent; most of the glow peaks are in or near saturation at these doses. The higher the β-dose at which a peak saturates, the higher is the α-efficiency (at low doses) of that peak. The results support the interpretation that the α-efficiency is low because the phosphor is near or in saturation in the localized region near the α-path. This interpretation is given quantitative support by a theoretical calculation of the localized energy-density.     

A Fiber-Optic Evanescent Wave O<Subscript>2</Subscript> Sensor Based on Ru(II)-Doped Fluorinated ORMOSILs

A novel fiber-optic evanescent wave sensor (FOEWS) for O₂ detection based on [Ru(bpy)₃]²⁺-doped hybrid fluorinated ORMOSILs (organically modified silicates) has been developed. The sensing element was fabricated by dip-coating the optical fiber with [Ru(bpy)₃]²⁺-doped hybrid fluorinated ORMOSILs composed of n-propyltrimethoxysilane (n-propyl-TriMOS) and 3, 3, 3-trifluoropropyltrimethoxysilane (TFP–TriMOS). Fluorophores of [Ru(bpy)₃]²⁺ were excited by the evanescent wave field produced on the fiber core surface and the emission fluorescence was quenched by O₂. Spectroscopic properties have been characterized by FTIR and UV–VIS absorption measurements. By using the presented hybrid fluorinated ORMOSILs, which enhances the coating surface hydrophobicity, the quenching response is increased. The sensitivity of the sensor is 7.5, which is quantified in terms of the ratio I _N2/I _O2 (I _N2 and I _O2 represent the fluorescence intensities in pure N₂ and pure O₂ environments, respectively). The limit of detection (L.O.D.) is 0.01% (3σ) and the response time is about 1 s. Meanwhile, the proposed FOEWS has the advantages of easy fabrication, low cost, fast response and suitable sensitivity for oxygen monitoring using a cheap blue LED as light source and coupling a miniature PMT detector directly to the optical fiber probe.     

Bound state solutions of the two-electron Dirac-Coulomb equation

We present a variational method for solving the two-electron Dirac-Coulomb equation. When the expectation value of the Dirac-Coulomb Hamiltonian is made stationary for all possible variations of the different components of a well-behaved trial function one obtains solutions representative of the physical bound state wave functions. The ground state wave function is derived from the application of a minimax principle. Since the trial function remains well-behaved, the method remains safe from the twin demons of variational collapse and continuum dissolution. The ground state wave function thus derived can be interpreted as a linear combination of different configurations. In particular, the admixing of intermediate states having one (two) electron(s) deexcited to a negative-energy orbital (orbitals) contributes a second-order level shiftE ₀₋ ⁽²⁾ which can be identified with the second-order shift due to the Pauli blocking of the production of one (or two) virtual electron-positron pair(s). Thus the minimax solution corresponds to the renormalized ground state in quantum electrodynamics, with deexcitations to negative-energy orbitals taking the place of the avoidance of virtual pairs. If one extends the relativistic configuration interaction (RCI) treatment by additionally including negative-energy and mixed-energyeigenvectors of the Dirac-Hartree-Fock hamiltonian matrix in the two-electron basis, the calculated energy will be shifted from the conventional RCI value by an amount that is much smaller thanE ₀₋ ⁽²⁾ . For two-electron atoms, we have derived expressions for the all-spinor limit (δE) and thes-spinor limit (δE _s) of this shift in leading orders. The all-spinor limit (δE) is of orderα ⁴ Z ^{4 1/3} whereas thes-spinor limit (δE _s) is of orderα ⁴ Z ^{3 2/3}. leading components are related to the 1-pair component ofE ₀₋ ⁽²⁾ in a simple way, and the relationships offer the possibility of computing energy due to virtual pairs. Numerical results are discussed.     

Multiphonon contribution to the structure factor of metals

The structure factor of Na is calculated including two-phonon terms and the Debye-Waller factor. The result is compared with the one-phonon approximation usually employed to evaluate the electronic transport coefficients. This multiphonon contribution can amount to 13 per cent at the melting point and 10 per cent at room temperature in the transport sensitive region of wave vector 1.5 k_F < q < 2 k_F, where k_F is the Fermi wave vector. We conclude that calculations of electronic transport coefficients of metals intended to attain a precision better than 10 per cent above the Debye temperature must take into account the contributions of the Debye-Waller factor and the two phonon terms.     

Ab initio calculation of force constants and equilibrium geometries

Force constants of the molecules HF, NH₃, CH₄ and BH₄ ^- have been calculated ab initio by the force method with a 73/3 + 1 gaussian lobe basis set. The results, including a former calculation on H₂O, agree well with experiment: the average relative error is 12 per cent for the diagonal force constants and the average absolute error is 0·06 mdyn/Å for the off-diagonal ones. The trends are also correctly reproduced. It is concluded that ab initio calculations of this accuracy can help to solve a number of spectroscopic problems. Force constants of BH₄ ^- have been determined from a combination of spectroscopic and ab initio information. Geometries have been obtained with little computing work and show good agreement with experiment.     

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.     

Infra-red spectrum,structure and properties of the N2-Ar van der Waals molecule

The first spectroscopic observation of bound N₂-Ar van der Waals molecules has been achieved with a cryogenic long path cell maintained at 87 K. The infra-red spectrum exhibits prominent fine structure near the N₂ stretching frequency which is assigned to hindered internal rotation of N₂ within the weakly bound complex. An analysis of this fine structure yields a T-shaped equilibrium geometry in which the N₂ bond axis is perpendicular to the N₂-Ar van der Waals bond axis. The observed spectrum is shown to be consistent with an internal rotational barrier of 20 cm^-1 (57 cal/mole). Approximately 20 per cent of the bound species are trapped by this rotational barrier and acquire a locked semi-rigid structure. The remaining 80 per cent have ill-defined geometry and undergo hindered internal rotation. The rotational envelope of an infra-red fundamental is analysed to give an estimate of the N₂-Ar bond length as 3·9 Å.     

Continuous wave,distributed feedback diode laser based sensor for trace-gas detection of ethane

The development of a continuous wave (CW), thermoelectrically cooled (TEC), distributed feedback (DFB) laser diode based spectroscopic trace-gas sensor for ultra-sensitive and selective ethane (C₂H₆) concentration measurements is reported. The sensor platform used tunable diode laser absorption spectroscopy (TDLAS) based on a 2f wavelength modulation (WM) detection technique. TDLAS was performed with a 100 m optical path length astigmatic Herriott cell. For an interference free C₂H₆ absorption line located at 2976.8 cm⁻¹ a 1σ minimum detection limit of 240 pptv (part per trillion by volume) with a 1 second lock-in amplifier time constant was achieved. In addition, reliable and long-term sensor performance was obtained when operating the sensor in an absorption line locked mode.