Accurate intensity calibration for low wavenumber (−150 to 150 cm−1) Raman spectroscopy using the pure rotational spectrum of N2

We report on an accurate intensity calibration method for low wavenumber Raman spectroscopy. It uses the rotational Raman spectrum of N₂. The intensity distributions in the rotational Raman spectra of diatomic molecules are theoretically well established. They can be used as primary intensity standards for intensity calibration. The intensity ratios of the Stokes and anti‐Stokes transitions originating from the same rotational levels are not affected by thermal population. Taking the effect of rotation–vibration interactions appropriately into account, we are able to calculate these intensity ratios theoretically. The comparison between the observed and calculated ratios of the N₂ pure rotational spectrum provides an accurate relative sensitivity curve (error ~5 × 10⁻⁴) in the wavenumber region of −150 to 150 cm⁻¹. We determine the temperature of water solely from the low wavenumber Raman spectra, using a thus calibrated spectrometer. The Raman temperature shows an excellent agreement with the thermocouple temperature, with only 0.5 K difference. The present calibration technique will be highly useful in many applications of low wavenumber quantitative Raman spectroscopy. Copyright © 2015 John Wiley & Sons, Ltd.     

Meshless acoustic analysis using a weakly singular Burton-Miller boundary integral formulation

The Burton-Miller boundary integral formulation is solved by a complex variable boundary element-free method (CVBEFM) for the boundary-only meshless analysis of acoustic problems with arbitrary wavenumbers. To regularize both strongly singular and hypersingular integrals and to avoid the computation of the solid angle and its normal derivative, a weakly singular Burton-Miller formulation is derived by considering the normal derivative of the solid angle and adopting the singularity subtraction procedures. To facilitate the implementation of the CVBEFM and the approximation of gradients of the boundary variables, a stabilized complex variable moving least-square approximation is selected in the meshless discretization procedure. The results show the accuracy and efficiency of the present CVBEFM and reveal that the method can produce satisfactory results for all wavenumbers, even for extremely large wavenumbers such as k = 10 000.     

Effective wave propagation along a rough thin-elastic beam

Two methods for computing the complex-valued effective wavenumber of a rough beam in the context of linear time-harmonic theory are presented. The roughness of the beam is modelled as a continuous random process of known characteristic length and root-mean-square amplitude for either the beam mass or the beam rigidity. The first method is based on a random sampling method, with the effective wave field calculated as the mean of a large ensemble of wave fields for individual realisations of the roughness. The individual wave fields are calculated using a step approximation, which is validated for a deterministic problem via comparison to results produced by an integral equation approach. The second method assumes a splitting of the length scale of the fluctuations and an observation scale, employing a multiple-scale approximation to derive analytical expressions for the effective attenuation rate and phase change. Numerical comparisons show agreement of the results of the random sampling method and the multiple-scale approximation for a wide range of parameters. It is shown that the effective wavenumbers only differ by a real constant between the cases of varying beam mass and rigidity.     

Development of a multi‐scale ocean model by using particle Laplacian method for anisotropic mass transfer

The direct injection of CO₂ into the deep ocean is one of the feasible ways for the mitigation of the global warming, although there is a concern about its environmental impact near the injection point. To minimize its biological impact, it is necessary to make CO₂ disperse as quickly as possible, and it is said that injection with a pipe towed by a moving ship is effective for this purpose. Because the injection ship moves over a spatial scale of O(10²km), a mesoscale model is necessary to analyse the dispersion of CO₂. At the same time, since it is important to investigate high CO₂ concentration near the injection point, a small‐scale model is also required. Therefore, in this study, a numerical model was developed to analyse CO₂ dispersion in the deep ocean by using a fixed mesoscale and a moving small‐scale grid systems, the latter of which is nested and moves in the former along the trajectory of the moving ship. To overcome the artificial diffusion of mass concentration at the interface of the two different grid systems and to keep its spatial accuracy almost the same as that in the small‐scale, a particle Laplacian method was adopted and newly modified for anisotropic diffusion in the ocean. Copyright © 2010 John Wiley & Sons, Ltd.     

Wavenumber Calibration of CCD Detector Raman Spectrometers Controlled by a Sinus Arm Drive

Abstract

The calibration procedures needed for use of dispersive Raman spectrometers have been reviewed. Like other high‐precision spectrometers incorporating moving gratings, Raman spectrometers are subject to problems with wavenumber scale accuracy. Commercially available Raman spectrometers of types DILOR‐HORIBA LabRam and RENISHAW System 1000 have been examined for wavenumber scale stability, linearity, and reproducibility. For reliable use of the wavenumber data, daily calibration is a necessity. A procedure to examine the linearity of such mechanical drive systems is presented. A new finding was that the examined spectrometers give wavenumber calibration errors that were quite reproducible from day to day at a given temperature in the laboratory but depended markedly on the selected setting of the gratings. Knowledge of this linearity problem is essential for obtaining a reliable calibration. The most correct calibration was obtained by the use of certain “golden” settings of the sinus drive at a constant temperature of the laboratory. In this way, the examined spectrometers could be used with better precision, without daily calibration, provided the temperature of the room was constant or corrected for. A procedure for correction of these errors by the software is suggested.     

Multilayer modeling of radiative transfer by SLW and CW methods in non-isothermal gaseous medium

Non-isothermal gaseous medium is modeled using the multilayer approach, breaking the one-dimensional system into a series of isothermal layers. Spectral integration of the radiative transfer equation (RTE) is performed for the spectral line weighted-sum-of-gray-gases and cumulative wavenumber approaches to modeling the spectral nature of the gas radiation. An exact analytical solution of RTE is obtained for the layers with both black and gray walls. Predictions show high accuracy, even with surprisingly few layers.     

CaxSr1—xS：Bi,Tm,Cu和CaS：Eu荧光材料的研究

所作的一部分工作是对长余辉的荧光材料ＣａｘＳｒ１－ｘＳＢｉ，Ｔｍ，Ｃｕ（ｘ＝０，０．７５，１）进行了研究．ＣａＳ和ＳｒＳ两种基质材料高温互溶后，因为基质的晶体微结构上的变化引起Ｂｉ３＋离子荧光效应的变化，即发光的发射波数发生改变．另一部分工作是对ＣａＳＥｕ加入陷阱机制后发光效应的研究．新的陷阱机制的引进，使得其余辉效应有较大的延长．     

Changes in spectral features with varying mole fractions of anisaldehyde in binary mixtures

Raman and IR spectra of neat anisaldehyde (4‐methoxybenzaldehyde (4MeOBz)) and its binary mixtures (in polar and nonpolar solvents) with varying mole fraction of 4MeOBz were investigated. The concentration dependence of the wavenumber position and line width (full width at half maximum, FWHM) was analyzed to study the interaction of the solute vibrational modes with the microscopic solvent environment. The wavenumbers of Raman modes of 4MeOBz, namely, the carbonyl stretching, aldehydic δ (C H) and ring‐breathing modes, showed a linear variation in the peak position for varying concentrations of 4MeOBz in the different solvents. The dependence of Raman line width with concentration of 4MeOBz of these modes was also taken into account. The solute–solvent interaction is stronger in 2‐propanol and acetonitrile because of the formation of hydrogen bonds between them, whereas in benzene the interaction is too weak to affect the Raman modes. The modes, ν (CO) in 2‐propanol and aldehydic δ (C H) in acetonitrile, gave a Gaussian‐type line width variation, which was explained by the concentration fluctuation model, and the linear variation of the line widths was also interpreted by solute–solvent interactions. IR spectra were taken for these binary mixtures, which also give further support to these data. Copyright © 2006 John Wiley & Sons, Ltd.     

Notes on Convection in a Porous Medium: (i) an Effctive Rayleigh Number for an Anisotropic Layer, (ii) the Malkus Hypothesis and Wavenumber Selection

Studies of convection in a layer of a saturated anisotropic porous medium uniformly heated from below are reviewed. Emphasis is placed on the usefulness of an effective Rayleigh number, defined (for certain boundary conditions) as the square harmonic-mean square root of horizontally-based and vertically-based Rayleigh numbers. The status of the Malkus hypothesis, together with its relationship with observed cell size, is also discussed. A possible explanation is provided for the observed phenomenon that in a porous medium the cell size decreases as the amplitude of convection increases, whereas in a clear fluid the cell size increases.