Evaluation method for Raman depolarization measurements including geometrical effects and polarization aberrations

In this article, we address the notoriously difficult problem to quantitatively link measured Raman depolarization values to theoretical polarizability tensor quantities, since quantum calculations do not incorporate experimental parameters. For this, we introduce a numerical model to calculate, for realistic experimental configurations, effective Raman line strength functions, Φ, which find their way into depolarization ratios, ρ. The model is based on interlinked integrations over the angles in the light collection path and a finite Raman source volume along the excitation laser beam. The model deals also with the conditional aperture parameters, associated with more than one optical component in the light collection path. Finally, we also can take into account polarization aberrations introduced by the sample cell windows. The procedure was fully tested for Raman depolarization spectra of selected hydrogen isotopologues. Distinct aspects affecting Raman depolarization data were validated, namely: (1) excitation polarization impurities; (2) extended Raman excitation volumes; (3) Raman light collection over finite solid angles; and (4) polarization aberrations introduced by optics in the light collection path. The correction of the experimental measurement data for the aforementioned effects resulted in depolarization ratios for the Q₁(J " ) Raman lines of H₂ and T₂, which mostly differed by less than 5% from those obtained by quantum‐calculations. Copyright © 2013 John Wiley & Sons, Ltd.     

General expression for the depolarization ratio for first‐order collision‐induced light scattering

A general expression that involves only the ranks of the molecular polarizabilties of the two molecules involved in a pair interaction yielding translational and rotational collision‐induced light scattering (CILS) is obtained. It may be used to investigate the behaviour of individual interactions that contribute to the incremental collision‐induced pair polarizability. Copyright © 2010 John Wiley & Sons, Ltd.     

Precise measurement of the depolarization ratio from photoacoustic Raman spectroscopy

A new method for the accurate determination of the Raman depolarization ratio is reported with an improved setup for photoacoustic Raman spectroscopy (PARS). The precise measurement is achieved by measuring the dependence of the acoustic signal intensity on the cross‐angle between the polarizations of two incident laser beams. We demonstrate this sensitive and simple method with several gaseous molecules, such as CH₄ and H₂. The measured results of depolarization ratios agree well with the theoretical values with an upper error limit of ± 0.005, which is comparable to that with polarization‐resolved CARS spectroscopy. Copyright © 2007 John Wiley & Sons, Ltd.     

Recovery of the depolarization ratio of single lines from overlapping isotropic and anisotropic Raman profiles and assignment of molecular vibrations,with special reference to toluene and toluene‐d8

If a Raman line consists of several overlapping components, any attempt to perform a quantitative analysis of the wavenumber‐dependent depolarization ratio ρ(ν) fails, since ρ(ν) of a composite line is not an additive function of ρ(ν) of its constituents, and for a composite line representing an envelope of i single lines, ρ_comp(ν) ≠ ∑ρ_i(ν). This situation causes significant difficulties in the analysis of Raman spectra, especially in the case of weak lines (overtones, combination bands, etc.) situated in the close vicinity of strong fundamentals. In this paper, a specific algorithm is employed to recover isotropic and anisotropic Raman profiles. Using toluene and toluene‐d₈ as examples, it is shown that the ρ(ν) spectra of all components of a composite spectrum can be easily restored, facilitating the assignment of overtones, hot bands, and combination bands. Copyright © 2006 John Wiley & Sons, Ltd.     

Nonadiabatic eigenvalues and adiabatic matrix elements for all isotopes of diatomic hydrogen

For all bound and quasibound levels of the ground electronic state of all six isotopes of diatomic hydrogen, wavefunctions obtained from the most recent ab initio potentials are used to calculate expectation values of the nuclear kinetic energy, of various powers of R, and of the average polarizability and polarizability anisotropy, together with the off-diagonal matrix elements of the polarizability required for predicting the intensities of Raman transitions for ΔJ = 0, ±2 and Δv = 0, −1, and −2. A scaling procedure for treating the nonadiabatic eigenvalue corrections is developed, which allows an extrapolation beyond results reported for H₂, HD, and D₂ to yield nonadiabatic level shift predictions for the three tritium isotopes. Features of this procedure which take account of implicit centrifugal distortion effects lead to significant improvements in the agreement between theory and experiment.     

Polarization‐resolved high‐resolution Raman spectroscopy with a light‐emitting diode

We demonstrate the use of a light‐emitting diode (LED) based experimental setup for collecting polarization‐resolved Raman spectra with good spectral resolution. The combination of a commercial red LED (630 nm), a 1‐nm bandwidth laser‐line filter, and a polarizing prism is used as a light source. Polarization‐resolved spectra in dimethyl sulfoxide are recorded and compared with the corresponding laser‐Raman spectra. The LED‐excited spectra exhibit a resolution slightly lower than those in the laser case but still close to the resolution of the spectrometer. All relevant spectral features of dimethyl sulfoxide including the symmetric and antisymmetric stretching modes of the CSC moiety are resolved with the experimental setup providing a spectral resolution of approximately 20 cm⁻¹. Copyright © 2013 John Wiley & Sons, Ltd.     

Laser-induced spark for simultaneous ignition and fuel-to-air ratio measurements

This work investigates the use of laser-induced gas breakdown for simultaneously igniting and measuring fuel-to-air ratio of CH₄–air and H₂–air combustible mixtures. The fuel-to-air ratio is determined using the measured spectral peak ratio I_o,Hα/I_o,OI. Sparks are produced using a single-mode, Q-switched Nd–YAG laser. The laser produces a beam of 6 mm in diameter at the wavelength of 1064 nm and pulse duration of 5.5 ns. The beam optics is designed to have mainly a beam splitter and a focusing lens. The beam splitter is coated to reflect the laser beam and transmit emission lines with wavelengths from 600 to 900 nm which are then collected by a fiberoptic cable and detected by an imaging spectrometer–detector assembly. The results showed a linear dependence of the spectral peak ratio on the equivalence ratio that can be generally expressed by φ=a(I_o,Hα/I_o,OI)+b, where a and b are the parameters that depend on the gas pressure. Using the least-square curve fitting technique to fit the experimental data, a calibration curve for calculating the equivalence ratio as a function of the ratio of (I_o,Hα/I_o,OI) was generated.     

Survival of molecular information under surfaced‐enhanced resonance Raman (SERRS) conditions

In the present paper, we discuss the molecular information that can be derived from surface‐enhanced resonance Raman Scattering (SERRS) experiments performed with different excitation wavenumbers, which are close to resonance with an excited electronic state of the molecule [surface‐enhanced Raman dispersion spectroscopy (SERADIS)]. We specifically consider the situation, where a molecule is physisorbed to a site characterized by a local electric field with a direction independent of the direction of the external, exciting field. The molecular information available in this experimental situation is compared with the information available in a corresponding Raman dispersion spectroscopy (RADIS) experiment performed on a free molecule or a molecule physisorbed to a site, where the local field is isotropic. The consequences for resonance Raman scattering (RRS) and RADIS, when the molecule is adsorbed in the highly anisotropic hot spot (HS), are discussed; here it is shown that only the molecular information originating from the symmetric part of the scattering tensor can survive in SERRS and in SERADIS. Besides, it is shown that the depolarization ratio can no longer be used to discriminate between totally and non‐totally symmetric modes in the polarized surface‐enhanced Raman scattering (SERS) spectra. These results have implications for the resonance Raman spectra, but even more important for the application of the resonance Raman effect in the investigation of excited vibronic molecular states, in general, and in the investigation of electronic states in larger bio‐molecules, such as the various metallo‐porphyrins. Copyright © 2009 John Wiley & Sons, Ltd.     

三波长宽角度消偏振平板分光膜的设计

分光膜都是倾斜使用的,不可避免地存在S和P 2个偏振分量的分离。在许多实际应用中,这是一个迫切需要解决的刺手难题。基于Thelen和Costich理论,选择初始膜系材料和结构,并在Needle合成法与Conjugate graduate精炼法的帮助下,采用全介质材料设计了532nm,633nm和1315nm三波长宽角度消偏振平板型分光膜,空气中入射角的变化范围为45°±5°。结果表明：在宽角度范围内,此膜系在(532±10)nm,(633±10)nm和(1315±10)nm范围的偏振分离都能比较好地满足消偏振要求。     

New expressions for depolarization dyadics in uniaxial dielectric-magnetic media

We present some novel expressions for the depolarization dyadics in uniaxial dielectric-magnetic media. These expressions were obtained by generalizing the Fikioris approach for extracting the singular behaviour of integrals involving the dyadic Green functions and the source current density distributions. Cubical, cylindrical and spherical geometries serve as examples for a discussion of the depolarization dyadics' dependence on geometry and anisotropy.     

Simultaneous acquisition of all four forms of circular polarization Raman optical activity: results for α‐pinene and lysozyme

A new circularly polarized (CP) Raman spectrometer is described that demonstrates simultaneous acquisition of all four forms of circular polarization Raman optical activity (ROA). The instrument is a design extension of a commercially available back scattering circular polarization (SCP) ROA spectrometer. Circular polarization of the incident beam is introduced with a quarter‐wave plate, and a half‐wave plate alternately positioned in and out of the beam controls the modulation between right circular polarization (RCP) or left circular polarization (LCP) states. Combining this modulation with the simultaneous detection of RCP and LCP scattered Raman radiation allows the measurement of incident circular polarization (ICP), SCP, in‐phase dual circular polarization(DCP_I) and out‐of‐phase DCP_II‐ROA. In addition, three different forms of backscattered Raman spectra, namely unpolarized, highly polarized, and depolarized Raman spectra, as well as a degree of circularity spectrum are obtained. The performance of the new all‐CP ROA spectrometer is evaluated with neat α‐pinene and aqueous hen lysozyme solution. Copyright © 2011 John Wiley & Sons, Ltd.     

Compensated Polarization Scrambler for Raman Depolarization and Intensity Measurements on Microsamples

It has long been recognized ^1,2,3,4,5 in measuring relative intensities and depolarization ratios of Raman lines that prism and grating spectrometers have different transmittances for light polarized parallel (T_∥) and perpendicular (T_⊥) to the slit. Several methods have been used to give equal instrument response to parallel and perpendicular polarization. Stitt and Yost³ used a Nicol prism parallel to the high-transmittance direction of the spectrometer, combined with a rotatable mica half-wave plate to transmit either vector to the Nicol prism. This method has the advantage of having a higher spectrometer transmittance, but the mica plate gives exact half-wave retardation at only a single wavelength. A mica quarter-wave plate ^4,5 averages the transmittances of the spectrometer for the two polarization directions, but is also wavelength dependent. Virtually achromatic circular polarizers have been designed and constructed ^6,7, but these devices are too bulky and expensive for the clear apertures needed for fast spectrometers.     

A spectroscopic study of water vapor isotopologues H2O, H2O and HDO using a continuous wave DFB quantum cascade laser in the 6.7 μm region for atmospheric applications

A quantum cascade spectrometer was used in the laboratory to study H₂¹⁶O, H₂¹⁸O and HDO line intensities near 6.7 μm. The spectral region ranging from 1483 to 1487 cm⁻¹, which is suitable for the in situ laser sensing of these isotopologues in the atmosphere, was investigated using a continuous-wave distributed feed-back quantum cascade laser. Eight lines of water vapor isopologues were studied—one line of the ν₂ band of H₂¹⁶O, one line of the 2ν₂-ν₂ band of H₂¹⁶O, two lines of the ν₂ band of H₂¹⁸O and four lines of the ν₂ band of HDO were carefully revisited. The measured intensities were thoroughly compared to relevant molecular databases and other experimental and calculated results. We also observe that the H₂O, D₂O, HDO equilibrium constant agrees excellently with previously determined values.     

无源光接入网单纤三向消偏振截止滤光片的研制

无源光接入网单纤三向技术是实现音频、视频、数据集成传输的关键技术。由于单纤三向滤波要求薄膜器件是大角度入射,因而所造成的偏振分离限制了信道的分离。在单纤三向滤光片的设计中,通过运用消偏振截止设计的方法,经过理论分析,并在莱宝APS1104机上镀膜,研制出了入射角为45°时偏振分量截止位置重合的消偏振截止滤光片,消除了偏振截止分离的影响。     

Fundamental vibrational frequencies and spectroscopic constants for the methylperoxyl radical,CH3O2, and related isotopologues 13CH3OO,CH3 18O18O,and CD3OO

Accurate spectroscopic and geometric constants for CH₃O₂, and its isotopologues ¹³CH₃OO, CH₃ ¹⁸O¹⁸O and CD₃OO, are predicted. Employing coupled cluster theory with single, double, and perturbative triple excitations [CCSD(T)], we obtain optimized equilibrium geometries using Dunning's cc-pVTZ basis set. A Taylor expansion of the potential energy surface, including all third-order and semidiagonal fourth-order terms in a basis of normal coordinates, yields anharmonic vibrational frequencies and vibrationally-averaged properties including the effects of anharmonicity. We detail the strong influence of Fermi resonances on the problematic ν₆ vibrational mode of CD₃OO, arriving at a value of 993?cm^?1; two previous experimental measurements of this mode appear to have been incorrectly assigned. Our computed energies for the low intensity ν₁₁ transition are in excellent agreement with experimental measurements performed for CH₃ ¹⁸O¹⁸O and CD₃OO, inspiring confidence that our results will serve as a guide for experimental measurement of this yet-unobserved quantity for the CH₃OO and ¹³CH₃OO isotopologues. Given the reliability of our force field, and considering the results of other experiments, we make a number of reassignments to previously recorded spectra, which eliminate large disagreements between experimental observations. The vibrational averaging of the rotational constants and geometries are also discussed for each isotopologue.     

Facility for preparation of gas mixture in muon catalyzed fusion experiments

A facility is described that allows safe handling of high tritium gas activity as dozens kilocuries in a regular laboratory environment. It is used to make and deliver into the target a mixture of specific isotopic composition with the contamination requirement of 10^-7 v.f. for Z>1 elements, and recover it upon completion of operation. With this facility, efforts have been accomplished to investigate into the muon catalyzed fusion on two targets – liquid tritium and high-pressure tritium types. Also, the operation range was 0.1–120 MPa for pressure and 20–800 K for temperature and the amount of tritium used was about 100 kCi. The facility showed reliability in operation without indications of radiation beyond the safety level. This revised version was published online in August 2006 with corrections to the Cover Date.     

An iterative calculation to derive extinction-to-backscatter ratio based on lidar measurements

The aerosol optical thickness (AOT) is an important parameter for understanding the radiative impact of aerosols. AOT based on lidar measurements is often limited by its finite detection range. In this paper, we have reported a method of fitting and iterative calculation to derive the extinction profile of background aerosols from 0 to 30 km at 532 nm, which is virtually the AOT of the entire atmosphere. The mean extinction derived from this method at the ground level tallies with visibility measurement and it is also consistent with the sun-photometer data, within experimental error. These data have been further treated to study the dust cases. For most of the cases, transmission losses were determined to estimate the extinction as well as lidar ratio. The result of the analysis shows that for background aerosols, a mean lidar ratio of 47±15 sr was found. For dust layers, a mean lidar ratio of 44±19 sr and an optical thickness of 0.53±0.49 were determined at 532 nm.     

New trend for optical signal-to-noise ratio of disturbed Raman fiber amplifier

In a distributed Raman fiber amplifier (DRFA), Raman amplification allows a lower signal launch powers to transverse the span above the noise floor while still increasing the optical signal-to-noise ratio (OSNR). It improves the noise figure and reduces the nonlinear penalty of fiber systems. In this paper, we demonstrate a new trend of OSNR at different pump configurations: forward, backward and bidirectional pumping for DRFAs as a function of fiber length. We also present the variation of OSNR with both input pump power and input signal power. It is found that forward pumping provides the highest OSNR, reaching its maximum value of 37 dB. However, backward pumping provides the smallest OSNR that has its maximum of 22 dB and the bidirectional pumping provides the moderate OSNR between the others having its peak of 26 dB.     

气相二氧化碳分子拉曼退偏比的准确测量

利用灵敏的光声拉曼光谱技术对气相二氧化碳分子在1240～1430 cm^-1振动光谱的拉曼退偏比进行了测量. 通过测量并拟合光声拉曼信号强度随两束入射光偏振方向夹角的变化,得到了比文献报道中更为精确的退偏比数据.