Direct measurement of the Rayleigh scattering cross section in various gases

Using the laser-based technique of cavity ring-down spectroscopy extinction measurements have been performed in various gases straightforwardly resulting in cross sections for Rayleigh scattering. For Ar and N₂ measurements are performed in the range 470-490 nm, while for CO₂ cross sections are determined in the wider range 470-570 nm. In addition to these gases also for N₂O, CH₄, CO, and SF₆ the scattering cross section is determined at 532 nm, a wavelength of importance for lidar applications and combustion laser diagnostics. In O₂ the cross section at 532 nm is found to depend on pressure due to collision-induced light absorption. The obtained cross sections validate the cross sections for Rayleigh scattering as derived from refractive indices and depolarization ratios through Rayleigh's theory at the few %-level, although somewhat larger discrepancies are found for CO, N₂O and CH₄.     

Bimodal dependence of light scattering/fluctuations on the concentration of aqueous solutions

Two concentration ranges (from 10^?5 to 10^?9 and from 10^?13 to 10^?18 M) corresponding to enhanced fluctuations of Rayleigh and Raman scattering of second-harmonic (527 nm) pulses of YVO₄:Nd³⁺ laser are found for aqueous solutions of antioxidant potassium phenosan. A correlation is revealed between the rise in elastic Rayleigh scattering intensity and its fluctuations and the shift of the center of OH Raman band of water toward the ice component characteristic frequency (3200 cm^?1). The development of phase-equilibrium instabilities is analyzed based on the model of fluctuations of the number of hydrogen bonds on the assumption of formation/destruction of ordered hydration layer of phenosan molecules in water.     

Messung der Spinabhängigkeit der Rayleighstreuung mit Hilfe der Interferenz von Mößbauer- und Rayleighstreuung

The interference of Mößbauer scattering and Rayleigh scattering was examined and it was found that this interference can be easily observed on certain conditions. The experiment was initially carried out with a single-line transition of the 14 keV energy level of Fe⁵⁷. From the experimental data the contribution of Rayleigh scattering could be determined relative to Mößbauer scattering and it could be shown that by measuring the interference of Mößbauer scattering and Rayleigh scattering one will have a sensitive detector for Rayleigh scattering. This was used to test the spin dependence of Rayleigh scattering. For this purpose, a similar experiment was carried out with circularly polarizedγ-quanta and polarized electrons, making use of the splitting of the Fe⁵⁷ hyperfine structure. By comparison of the measured values for left-handed and right-handed circularly polarized components a strong spin dependence of the Rayleigh scattering was found.     

Molecular orientation correlations and reorientational motions in liquids carbon monoxide,nitrogen and oxygen at 77 K; A Raman and Rayleigh light-scattering study

Reorientational autocorrelation functions have been determined from measurements of depolarized vibrational Raman scattering for liquid carbon monoxide, nitrogen and oxygen at 77 K and atmospheric pressure. The autocorrelation functions, which for these liquids are not significantly affected by vibration-rotation interaction, reveal that free rotation is an important feature of the molecular motion in liquid nitrogen but is less important for carbon monoxide and oxygen. The differences in behaviour are discussed in terms of intermolecular forces.

New values for the depolarized Rayleigh scattering cross section have been determined from intensity measurements made relative to the 992 cm^-1 Raman line of benzene. These values are compared to those reported previously by the authors using a different intensity standard (Chem. Phys. Lett., 31, 355 (1975)). The scattering cross sections yield the following values , where ?_ij is the angle between the major axes of molecules i and j (i≠j) and P ₂ indicates the second Legendre polynomial: -0·15 ± 0·2 for CO, +0·30 ± 0·2 for N₂ and +0·40 ± 0·2 for O₂. The large errors result from uncertainties in the local field correction factor. The negative value for CO can be explained as a result of strong quadrupole interactions which tend to align neighbouring molecules perpendicular to one another. The forms of the reorientational cross-correlation functions determined from the current Raman data and previous Rayleigh data are briefly discussed.     

Photon interaction cross-sections and anomalous scattering factors of Cu and Ag

Total attenuation cross sections of copper and silver have been measured in the energy range 5 to 85 keV in a narrow beam good geometry set up using X- andγ-rays emitted from radio isotopes, by employing a high resolution hyper pure germanium detector. From the measured values, the photoeffect cross-sections have been derived by subtracting a small contribution of the sum of the theoretical coherent and incoherent scattering cross sections. The photoeffect cross-sections so obtained are found to be in better agreement with the unrenormalized values of Scofield [10]. These photoeffect cross-sections have been used to evaluate the dispersion corrections (also called anomalous scattering factors)f ⁺ andf″ for the forward Rayleigh scattering amplitude by a numerical evaluation of the dispersion integral that relates them at the energies at which the cross-sections have been measured. To thef ⁺ values so obtained, the relativistic corrections proposed by different investigators are included separately and the valuesf′ so obtained are compared with the available data and discussed. Possible conclusions are drawn from the present study.     

Molekularstrahlmessungen von Stoßquerschnitten für Übergänge zwischen definierten Rotationszuständen zwei-atomiger Moleküle

Inelastic collision cross sections for transitions between specified rotational states designated by (J, M) have been measured in a molecular beam apparatus. With an electrostatic four pole field molecules in a specified rotational state are separated out of a molecular beam and focussed into a gas filled scattering chamber. Molecules which have been scattered by less than 1/2° are then collected in a second four pole field, located directly behind the scattering chamber, and are analyzed for their rotational state. From a comparison of the measured pressure dependence with calculated curves a determination of inelastic collision cross sections for specified quantum jumps is possible. Measured inelastic scattering cross sections for the transitions (2,0→3,0) are reported for the gases He, Ne, Ar, Kr, CH₄, SF₆, H₂, O₂, Air, N₂O, H₂O, CF₂Cl₂. The values range between about 5 and 100 Ų in the order indicated. The scattering gases NH₃ und ND₃ yielded larger cross sections of about 600 Ų and, in addition, the transitions (3,0)→(2,0),(1,0)→(2,0), (2,0)→(1,0) and (3,0)→(1,0) were observed. Total cross sections for the same gases were also measured with the apparatus.     

Molecular motion in supercooled glycerol

Quasi-elastic Rayleigh scattering of 14·4 keV photons has been measured on supercooled liquid glycerol at -30°C and 0°C by employing the Mössbauer effect. Total scattered intensity, quasi-elastically scattered intensity I _q and energy width of I _q(k, ω) have been determined for k=0·6 to 4·2 Å^-1. The molecular motion is modelled as: random-walk diffusional motions for the centre-of-mass translation and for the orientation of independent rigid molecules, plus fast-bounded translational jitter (vibration). The model parameters are evaluated. The temperature dependence of the translational diffusion constant corresponds to an activation energy of 12 kcal/mol. Comparison is made especially with N.M.R. results for rotational motion. The effect of orientational jitter (libration) is considered and its possible influence on nuclear magnetic relaxation is pointed out.     

Dependence of the Compton to Rayleigh intensity ratio on the scatterer atomic number in the range of 4(Be) to 31(Ga)

Compton to Rayleigh scattering intensity ratios (I_C/I_R) have been measured using X-rays with energy 17.44 keV for single-component materials with atomic number Z from 4 (Be) to 31 (Ga) and binary compounds of stoichiometric composition. The measurements have been performed using two optical schemes: an energy-dispersive X-ray fluorescence scheme with a molybdenum secondary target and wavelength-dispersive X-ray fluorescence one. The processing of the spectra was carried out by fitting with Pearson VII functions. For single-component and binary standards, the experimental dependence of the scattering intensity ratio on the atomic number was found to be the same. This confirms the additivity of the contribution of different atoms to the scattering. The dependence has a complex shape but is well described by the theoretical relationship for I_C/I_R with correction on the difference between Compton and Rayleigh radiation absorption coefficients. Two ranges of atomic number values are defined, in which the effective atomic number Z_eff can be determined by the calibration method using this dependence: for Z from 4 to 7 with low error of ΔZ_eff =±0.15 and for Z_eff from 10 to 18 with low error of ΔZ_eff =±0.69. A change in the shape of the Compton peak and an overestimated value of the of the Compton and Rayleigh peak intensity ratio when passing from a single-component scatterer (Al or Si) to their oxides Al₂O₃ or SiO₂, respectively, have been revealed.     

The effect of choice of basis set in molecular pseudopotential calculations

The long tails at high Stokes and anti-Stokes frequencies observed in Rayleigh scattering from compressed methane, carbon tetrafluoride and sulphur hexafluoride are attributed to induced rotational transitions. The longest-range contribution to the collision-induced polarizability, the dipoleinduced-dipole term in R ^-3, where R is the separation of a pair of molecules, does not fluctuate with molecular rotation. However, the dipole-quadrupole polarizability A of the tetrahedron leads to a rotating contribution in R ^-4. The dipole-octopole polarizability E of an octahedron and a tetrahedron leads to a contribution in R ^-5 which also rotates with the molecule. The rotational transitions associated with these polarizabilities can explain both the intensity and the shape of the long tails. Approximate values of A for CH₄ and CF₄ and of E for SF₆ are deduced. As in the monatomic case, there is a simple relationship between the total scattered intensity and the second Kerr virial coefficient.     

Photolysis rate coefficients in the upper atmosphere: Effect of line by line calculations of the O2 absorption cross section in the Schumann-Runge bands

A line by line (LBL) method to calculate highly resolved O₂ absorption cross sections in the Schumann-Runge (SR) bands region was developed and integrated in the widely used Tropospheric Ultraviolet Visible (TUV) model to calculate accurate photolysis rate coefficients (J values) in the upper atmosphere at both small and large solar zenith angles (SZA). In order to obtain the O₂ cross section between 49,000 and 57,000 cm⁻¹, an algorithm which considers the position, strength, and half width of each spectral line was used. Every transition was calculated by using the HIgh-resolution TRANsmission molecular absorption database (HITRAN) and a Voigt profile. The temperature dependence of both the strength and the half widths was considered within the range of temperatures characteristic of the US standard atmosphere, although the results show a very good agreement also at 79 K. The cross section calculation was carried out on a 0.5 cm⁻¹ grid and the contributions from all the lines lying at ±500 cm⁻¹ were considered for every wavelength. Both the SR and the Herzberg continuums were included. By coupling the LBL method to the TUV model, full radiative transfer calculations that compute J values including Rayleigh scattering at high altitudes and large SZA can now be done. Thus, the J values calculations were performed for altitudes from 0 to 120 km and for SZA up to 89°. The results show, in the J_O2 case, differences of more than ±10% (e.g. at 96 km and 30°) when compared against the last version of the TUV model (4.4), which uses the Koppers and Murtagh parameterization for the O₂ cross section. Consequently, the J values of species with cross sections overlapping the SR band region show variable differences at lower altitudes. Although many species have been analyzed, the results for only four of them (O₂, N₂O, HNO₃, CFC12) are presented. Due to the fact that the HNO₃ absorption cross section extends up to 350 nm this molecule was used to verify the consistency of the new TUV-LBL at lower altitudes. Thus, it shows differences up to 5.7% at 21 km but 0% in the troposphere. Because of the more accurate consideration of the Rayleigh scattering the distribution of the actinic flux in its direct and diffuse components (in the SR bands wavelength interval) is also modified.     

Site-selective detection of vibrational modes of an iron atom in a trinuclear complex

Nuclear inelastic scattering (NIS) experiments on the trinuclear complex [⁵⁷Fe{L-N₄(CH₂Fc)₂} (CH₃CN)₂](ClO₄)₂ have been performed. The octahedral iron ion in the complex was labelled with ⁵⁷Fe and thereby exclusively the vibrational modes of this iron ion have been detected with NIS. The analysis of nuclear forward scattering (NFS) data yields a ferrous low-spin state for the ⁵⁷Fe labelled iron ion. The simulation of the partial density of states (pDOS) for the octahedral low-spin iron(II) ion of the complex by density functional theory (DFT) calculations is in excellent agreement with the experimental pDOS of the complex determined from the NIS data obtained at 80 K. Thereby it was possible to assign almost each of the experimentally observed NIS bands to the corresponding molecular vibrational modes.     

CoFe2O4纳米粒子的共振散射光谱研究

液相纳米粒子CoFe2O4在400，470，510，800和940nm产生五个共振散射峰。它是一种非线性光散射介质。当激发波长为330nm时，CoFe2O4纳米粒子分别在于330，660和990nm产生一个共振散射峰、一个1/2频散射峰和一个1/3分频散射峰；当激发波长为800nm时，在800nm产生一个共振散射峰，而在400nm产生一个较该共振散射峰更强的2倍频散射峰。分频散射和倍频散射与共振散射有相似的散射行为。根据建立的灰白粒子体系共振散射光谱原理定性解析了CoFe2O4纳米粒子体系的共振散射光谱。     

Accurate ionization energy values for the transitions O2+,X2Πg(v′= 0-20) ← O2,X3Σg− (v″ = 0) and molecular constants of oxygen ground ionic state,determined by Ne(I) (73.6 nm) photoelectron spectroscopy

High resolution Ne(I)(73.6 nm) photoelectron spectroscopic measurements provide accurate values of the ionization energies for the first 21 vibrational levels of O₂⁺,X²Π_g, From these data molecular constants have been derived for the ground state of the oxygen ion O₂⁺.     

Many-body correlations for Raman and Rayleigh collision induced scattering

In this paper, the spectral shape of the collision induced scattering is calculated in the dipole-induced-dipole approximation for the Raman symmetric vibrational band of optically isotropic molecules. Comparison is made with Rayleigh results. Experimental data for Rayleigh and v ₁ Raman band of CF₄ are discussed.     

Comparison of theoretical and experimental red and near infrared absorption spectra in overheated potassium vapour

The K₂ molecular spectra have been theoretically and experimentally investigated in the wavelength range between 550 nm and 1100 nm and at the temperatures between 650 K and 1100 K. Semiclassical theoretical simulations were performed using the most recent data for the potential energy curves for the K(4S)+K(4S) and K(4S)+K(4P) systems and the relevant dipole transition moments. The measurements of the corresponding spectra were performed by a spatially resolved absorption method in an inhomogeneous overheated potassium vapour generated in a heat pipe. Both theoretical and experimental investigations confirmed that the reduced absorption coefficients of the potassium diffuse triplet bands at 575 nm, 721.5 nm and 1095 nm are practically independent of temperature in a wide temperature range. The obtained data for the reduced absorption coefficients of these bands can be used for a simple and accurate determination of potassium atom number densities in the range from 5×10¹⁶ cm^-3 to 5× 10¹⁸ cm^-3.     

Observation of intense stokes and anti-stokes lines in CH4 pumped by 355 nm of a Nd:YAG laser

The stimulated Raman scattering (SRS) and four-wave mixing (FWM) processes have been studied in detail in CH₄ gas pumped by the third-harmonic of Nd:YAG laser at =355 nm. The conversion efficiency and average output energy have been measured for the various Stokes and anti-Stokes lines at different experimental conditions. The threshold input energy at various CH₄ pressures has been calculated for the unguided and capillary waveguide Raman cells. The calculated values for the capillary case have been compared with the measured values at different CH₄ pressures and the two results are in good agreement.     

Condensation of monosilane-argon and monosilane-helium mixtures in free jets

Condensation of gaseous monosilane-argon and monosilane-helium mixtures was investigated in free jets by a Rayleigh scattering laser diagnostic technique. The condensation of a SiH₄-Ar mixture begins to develop at a lower stagnation pressure and at a shorter distance from the nozzle, and proceeds at a higher rate, as compared to condensation in monosilane-helium and pure argon jets. The results of Rayleigh scattering measurements in condensing monosilane-argon jets scale with the parameter P ₀ d ^0.8. An analysis of the results obtained in this study and found in literature suggests that simultaneous monosilane-argon condensation lead-ing to the formation of mixed clusters takes place in the monosilane-argon mixture.     

Rayleigh scattering in fused silica samples for gravitational wave detectors

Laser interferometer gravitational wave detectors require very high optical quality test masses. We report the bulk Rayleigh scattering in high quality fused silica samples. Results show that the scattering of the high quality fused silica is similar for various grades of fused silica from Heraeus. The total integrated scattering is about 0.7 ppm cm^− 1at 1064 nm wavelength, which agrees with the theoretical value calculated using known fused silica parameters. All samples show Rayleigh scattering ratio inhomogeneity of ~ 4%.     

Neutron Rayleigh and Brillouin scattering in normal 4He

Rayleigh and Brillouin peaks have been observed in neutron scattering by normal fluid ⁴He at 4.2 K and saturated vapour pressure in the wavevector transfer range from 0.06 Å^?1 to 0.2 Å^?1. The observations can be described by hydrodynamics, but there is a small discrepancy with the thermodynamic parameters.