Application of the Keating Bendings to the In-Plane Vibrations of Naphthalene and Benzene

An approximate force field was deduced for the in-plane vibrations of naphthalene in terms of five parameters corresponding to the coordinates: C-C and C-H stretchings, CCC (two types) and CCH Keating's bendings. Calculated frequencies were compared to observed data. On the other hand, these results were compared to those where Decius' bendings were applied. The set with Keating's bendings proved to be the superior one.

The corresponding force fields were applied to benzene, and the same general conclusion was reached.     

Boron Trifluoride: Application of the Keating Bendings to the Degenerate Vibrations

The harmonic force field of the E' species of BF₃ is studied. The Keating force field (KFF) is defined in analogy with the familiar VFF and CFF. In this connection three different coordinate sets are introduced. All of them contain bond stretchings. In addition, the valence coordinates include ordinary (Decius') bendings, the central coordinates nonbond stretchings, and Keating coordinates the Keating's bendings.

The experimental data of vibrational frequencies and Coriolis constants are reviewed extensively, as well as previous normal coordinate analyses. The different coordinate sets are tested for their usefulness as basis of force field approximations. For this purpose two different sets of experimental data are applied. The general conclusion goes in favour of the Keating coordinates.     

Planar Symmetrical XY3 and Boron Trihalides: Mean-Square Amplitudes and Keating Coordinates

The E' block of the mean-square amplitude matrix (Σ) for the planar symmetrical XY₃ molecular model is treated theoretically in terms of the Keating coordinates. A numerical example for ¹¹BF₃ is given. Also the mean amplitudes of vibration (ι) and Bastiansen-Morino shrinkage effect (Δ) are considered. New relations which connect the mean-square amplitudes and force constants are given. Previous works on mean amplitudes and related quantities for boron trihalides from vibrational spectroscopy and gas electron diffraction are reviewed, and some new calculations are reported.     

A Simple Force-Field Approximation Applied to the In-Plane Vibrations of Some Condensed Aromatics

In-plane vibrational frequencies of five condensed aromatics were computed from a five-parameter force field pertaining to stretchings and Keating's bendings. The molecules are: anthracene, phenanthrene, pyrene, chrysene and coronene. The results were compared with previous ones from a five-parameter approximation, which employs Decius' bendings. As far as the agreement between calculated and observed frequencies are concerned the results with Keating's bendings appeared clearly to be the superior ones in all the cases investigated.     

The Degenerate Vibrations of BCl3, BBr3 and BI3 with Application of Keating Coordinates

The experimental works of vibrational spectroscopy and normal coordinate analyses for BCl₃, BBr₃ and BI₃ are reviewed extensively. Harmonic force fields of the E' species are produced using isotopic frequencies and Coriolis constants as additional data, respectively. The usefulness of Keating coordinates versus valence coordinates as basis of force field approximations is discussed. The conclusions are not unequivocal, but they go in favour of the Keating coordinates when the reliability of the different computations is taken into account. Boron trichloride is treated specifically in some detail. Final force fields are proposed for the title molecules with the aid of the mass influence on Coriolis constants.     

Analysis of high-resolution infrared and CARS spectra of SO3

Three fundamental modes and several hot bands of ³⁴S¹⁸O₃ have been investigated using both infrared spectroscopy and coherent anti-Stokes Raman scattering spectroscopy (CARS). Coriolis coupling effects are particularly noticeable in ³⁴S¹⁸O₃ due to the close proximity of the ν₂ and ν₄ fundamental vibrations, whose wavenumber values are 477.50864(5) and 502.05565(4) cm⁻¹. The uncertainties in the last digits are shown in parentheses and are two standard deviations. Hot band transitions from ν₂, ν₄ levels give access to infrared inactive ν₂, ν₄ combination/overtone levels which interact strongly with levels of the Raman-active ν₁ symmetric stretching mode due to indirect Coriolis couplings, l-resonances, and Fermi resonances. The result is a complex ν₁ CARS Q-branch spectrum that is the most perturbed of the four SO₃ isotopomers we have studied. The relative importance of these interaction terms on the ν₁ CARS spectrum is examined in some detail and accurate rovibrational constants are determined for all of the mixed states, leading to deperturbed values of 1004.662(24), 0.0003503(9), and 0.0007066(12) cm⁻¹ for ν₁, α₁^B, and α₁^C, respectively. The B_e value is found to be 0.310875(12) cm⁻¹, which gives an equilibrium bond length r_e of 141.7339(3) pm, in excellent agreement with values of 141.7340(1) and 141.7347(7) pm reported earlier for ³²S¹⁶O₃ and ³⁴S¹⁶O₃.     

On the calculation of force constants using isotopic frequencies by parametric method: Application to systems of (3×3) order

A method is proposed for the determination of angle parameters for ONF, ONCl and ONBr, utilising the isotopic frequencies of two isotopically substituted molecules. The force constants, Coriolis coupling constants, inertia defect, mean amplitudes of vibration and rotational distortion constants were also calculated and compared with literature values.     

Evaluation for the configurational and electronic state of SO3 adsorbed on Pt surface

We evaluate the adsorption of SO₃ molecule on the Pt (1 1 1) surface using the first-principles calculations by a slab model with a periodic boundary condition. We find that there are four stable adsorption configurations on the Pt surface, where SO₃ molecules are adsorbed above the three-fold fcc and hcp sites. In two of these configurations, S and two O atoms are bound to the Pt atoms, and in two other of them, all the three O atoms are bound to Pt surface atoms. Besides, it is found that molecular orbitals of SO₃ and those of Pt surface are hybridized in the active metal d-bands region, that the localized molecular orbitals in SO₃ are stabilized, and that the charge is transferred from Pt to S 3p by SO₃ adsorption on Pt surface though the other interaction of S and O (bound to Pt) component with Pt is little. In addition, the bond between S and O bound to Pt become weak by SO₃ adsorption on Pt surface because the charge polarization to O-Pt bond weakens the bond between S and O bound to Pt. This interaction is assumed to encourage the breakage of S-O bond.     

On-line Sulfur Isotope Analysis of Organic Material by Direct Combustion: Preliminary Results and Potential Applications

Abstract

Sulfur isotopes have received little attention in ecology studies because plant and animal materials typically have low sulfur concentrations (< 1 wt.%) necessitating labor-intensive chemical extraction prior to analysis. To address the potential of direct combustion of organic material in an elemental analyzer coupled with a mass spectrometer, we compared results obtained by direct combustion to results obtained by sulfur extraction with Eschka's mixture. Direct combustion of peat and animal tissue gave reproducibility of better than 0.5‰ and on average, values are 0.8‰ higher than values obtained by Eschka extraction. Successful direct combustion of organic material appears to be a function of sample matrix and sulfur concentration. Initial results indicate that direct combustion provides fast, reliable results with minimal preparation. Pilot studies underway include defining bear diets and examining fluctuations between freshwater and brackish water in coastal environments.     

H2SO4-HAc-GIC的合成及其X射线衍射光谱和紫外光谱研究

本文以天然鳞片石墨为原料,合成了H2SO4－HAc-GIC,对该石墨层间化合物进行了X衍射及紫外光谱分析,测定了含硫量,并利用光谱分析结果对反应机理进行了初步探讨。     

The response of thermally and optically stimulated luminescence from Al2O3:C to high-energy heavy charged particles

The thermoluminescence (TL) and optically stimulated luminescence (OSL) response of Al₂O₃ dosimeters to high-energy heavy charged particles (HCP) has been studied using the heavy ion medical accelarator at Chiba, Japan. The samples were Al₂O₃ single-crystal chips, of the type usually known as TLD-500, and Luxel^TM dosimeters (Al₂O₃:C powder in plastic) from Landauer Inc. The samples were exposed to ⁴He (150 MeV/u), ¹²C (400 MeV/u), ²⁸Si (490 MeV/u) and ⁵⁶Fe (500 MeV/u) ions, with linear energy transfer values covering the range from 2.26 to 189 keV/μm in water and doses from 1 to 100 mGy (to water). A ⁹⁰Sr/⁹⁰Y beta source, calibrated against a ⁶⁰Co secondary standard, was used for calibration purposes. For OSL, we used both continuous-wave OSL measurements (CW-OSL, using green light stimulation at 525 nm) and pulsed OSL measurements (POSL, using 532 nm stimulation from a Nd:YAG Q-switched laser). The efficiencies (η_HCP,γ) of the different HCPs at producing OSL or TL were observed to depend not only upon the linear energy transfer (LET) of the HCP, but also upon the sample type (single crystal chip or Luxel^TM) and the luminescence method used to define the signal—i.e. TL, CW-OSL initial intensity, CW-OSL total area, or POSL. Observed changes in shape of the decay curve lead to potential methods for extracting LET information of unknown radiation fields. A discussion of the results is given, including the potential use of OSL from Al₂O₃ in the areas of space radiation dosimetry and radiation oncology.     

Dissociation Energies of CN,PbF, SiF,SnF, SnS and NBr MOLECULES

The ground state dissociation energies of CN, PbF, SiF, SnF, SnS and NBr molecules have been estimated using the empirical electronegativity potential function proposed by Szöke and Baitz. The dissociation energies for these molecules have been found to be 7.9, 3.2, 4.2, 3.2, 3.0 and 2,7 eV respectively and compared with the earlier values.     

The response of thermally and optically stimulated luminescence from Al2O3:C to high-energy heavy charged particles

The thermoluminescence (TL) and optically stimulated luminescence (OSL) response of Al₂O₃ dosimeters to high-energy heavy charged particles (HCP) has been studied using the heavy ion medical accelarator at Chiba, Japan. The samples were Al₂O₃ single-crystal chips, of the type usually known as TLD-500, and Luxel^TM dosimeters (Al₂O₃:C powder in plastic) from Landauer Inc. The samples were exposed to ⁴He (150 MeV/u), ¹²C (400 MeV/u), ²⁸Si (490 MeV/u) and ⁵⁶Fe (500 MeV/u) ions, with linear energy transfer values covering the range from 2.26 to 189 keV/μm in water and doses from 1 to 100 mGy (to water). A ⁹⁰Sr/⁹⁰Y beta source, calibrated against a ⁶⁰Co secondary standard, was used for calibration purposes. For OSL, we used both continuous-wave OSL measurements (CW-OSL, using green light stimulation at 525 nm) and pulsed OSL measurements (POSL, using 532 nm stimulation from a Nd:YAG Q-switched laser). The efficiencies (η_HCP,γ) of the different HCPs at producing OSL or TL were observed to depend not only upon the linear energy transfer (LET) of the HCP, but also upon the sample type (single crystal chip or Luxel^TM) and the luminescence method used to define the signal—i.e. TL, CW-OSL initial intensity, CW-OSL total area, or POSL. Observed changes in shape of the decay curve lead to potential methods for extracting LET information of unknown radiation fields. A discussion of the results is given, including the potential use of OSL from Al₂O₃ in the areas of space radiation dosimetry and radiation oncology.     

Nanoindentation of wet and dry compact bone: Influence of environment and indenter tip geometry on the indentation modulus

The indentation-derived elastic modulus, E, of bovine compact bone was obtained by nanoindentation. The indentation modulus of the dry condition (i.e. under atmospheric conditions) is 40% higher than when measured wet (i.e. immersed in buffer solution). Although this difference is independent of orientation, there is a 20% difference in the indentation modulus within the same tested environment between longitudinal and transversal directions. In addition, the estimated indentation modulus of the same samples when tested wet in buffer solution after deep freezing (?15°C) was not affected. The discrepancy between wet and dry results was attributed to the non-mineralized phase contribution and rationalized by a simple mechanical model [I. Jäger and P. Fratzl, Biophys. J. 79 (2000) p.1737]. Anisotropy effects could be explained in terms of deformation mechanisms with orientation. The effect of frozen storage temperatures may be clarified considering the biomechanics of the helicoidal arrangement of lamellar bone. Viscoelastic effects were also considered and incorporated into analysis of the force–displacement data.     

二组分食用混合油的线性混合模型研究与应用

基于二组分混和食用油的吸收系数是各自组分吸收系数按照掺杂比例的线性组合的假设以及朗伯-比尔吸收机理,提出并推导了二组分食用混合油的线性混合数学模型。该数学模型可根据相同厚度的两种原料油和其二组分混合油对相同光源的吸收光强变化计算出混合油的组分比例。根据误差理论,利用全微分公式分析了组分比例计算值的误差,表明通过选择使两种原料油的透射光强和吸光度差值的乘积较大的波长位置,可以优选出检测波长。搭建了可见-近红外光谱检测系统,利用花生油掺杂玉米油、花生油掺杂大豆油和玉米油掺杂大豆油三种混合油对模型进行了验证。结果表明,该模型对掺杂10%以上的混合油的成分比例计算值和实际值的相对误差在5%以内,相关系数分别达到0.999 4,0.999 7和0.999 3,标准误差分别为0.006 9,0.005 1和0.007 6,并证实本研究的波长选取方法是合理的。此外,对3种按同样比例组合的、未混合的分立油样本进行了检测,计算组合比的相对误差也可控制在10%以内,同时揭示入射光源的平行度和待测装置的垂直度对检测精度有一定影响。试验证明,不同于传统的光谱结合化学计量学的检测方法,本方法可以仅通过检测原料油和混合油在选定波长上的吸收光强即可准确计算得到掺杂比例。     

A look at the abandoned contributions to cosmology of Dirac,Sciama, and Dicke

The separate contributions to cosmology of the above researchers are revisited and a cosmology encompassing their basic ideas is proposed. We study Dirac's article (1938) on the large number hypothesis, Sciama's proposal (1953) of realizing Mach's principle, and Dicke's considerations (1957) on a flat‐space representation of general relativity with a variable speed of light (VSL). Dicke's tentative theory can be formulated in a way which is compatible with Sciama's hypothesis on the gravitational constant G. Additionally, such a cosmological model is shown to satisfy Dirac's second ‘large number’ hypothesis on the total number of particles in the universe being proportional to the square of the epoch. In the same context, Dirac's first hypothesis on an epoch‐dependent G – contrary to his prediction – does not necessarily produce a visible time dependence of G. While Dicke's proposal reproduces the classical tests of GR in first approximation, the cosmological redshift is described by a shortening of measuring rods rather than an expansion of space. Since the temporal evolution of the horizon R is governed by , the flatness and horizon problems do not arise in the common form.