Mössbauer Spectroscopic Study on Vertical Distribution of Iron Species in Sediments from Qinghai Lake,China

In this study, ⁵⁷Fe Mössbauer spectroscopy has been applied to sediments collected from Qinghai Lake in Qinghai Province, China, to investigate the vertical distribution of iron species. Their Mössbauer spectra consisted of four doublets ascribable to one paramagnetic high-spin Fe³⁺, two paramagnetic high-spin Fe²⁺ with different quadrupole splittings, and one diamagnetic low-spin Fe²⁺ that corresponds to pyrite (FeS₂). The distribution of pyrite suggested climatic changes during the past nine thousand years. It was demonstrated that the iron speciation in the salt lake sediments by Mössbauer spectroscopy can be used to reconstruct the past environment.

     

Measurement of Fluorescence Quantum Yield of Ultraviolet-Absorbing Substance Extracted from Red Alga: Porphyra yezoensis and its Photothermal Spectroscopy

Optical properties of an ultraviolet-absorbing substance (UVAS) extracted from the marine red alga, Porphyra yezoensis, have been investigated. The substance is excited by UV light, and the emitted fluorescence is detected using an intelligent fluorescence detector. The fluorescence of UVAS is weaker by four orders of magnitude than the fluorescence intensity emitted by anthracene in the same optical system. The absorbed energy is apparently not transferred to the photosynthesis process and is believed to be consumed as heat. Using photothermal spectroscopy, a signal is observed indicating that the absorbed photon energy has transferred to the heat. The waveform of the photothermal signal of UVAS is similar to that of quinoxaline, whose fluorescence quantum yield is known to be zero. It is determined that the fluorescence quantum yield and the energy of the triplet state of UVAS are 1.7 ± 0.7 ± 10⁻⁴ and 21000 ± 1000 cm ⁻¹, respectively. The conclusion is that the excited molecules of UVAS decay by passing through the triplet state and dissipate all absorbed energy as heat.     

Fe–Mn–Al–C Alloys: a Study of Their Corrosion Behaviour in SO2 Environments

The corrosion reaction of four Fe–Mn–Al alloys exposed to a cycling, dry–humid, SO₂ (0.001% by volume) polluted atmosphere was studied. ICEMS, XPS, AES-SAM and transmission Mössbauer spectroscopy at different temperatures were employed to characterize the corrosion products. The analytical results indicate that (i) ferrihydrite is the main component of the rust; (ii) there is an abundant presence of Mn²⁺ and SO₃ ^2–/SO₄ ^2– on the top of the corrosion layer, the concentration of SO₄ ^2– increasing with the number of cycles; and (iii) the magnetic hyperfine pattern exhibited by the series of low-temperature spectra of the rust is quite different from that observed in the rust formed under similar corrosive environments on iron and weathering steel. This latter finding is correlated with a slow rate of transformation of the Fe³⁺ species formed at the early stages of corrosion into -FeOOH, the usual final product of this type of corrosion processes. The sulphate anions, abundant inside the electrolyte during the wet periods, could be incorporated to the ferrihydrite structure being responsible for the Mössbauer spectral pattern recorded from the corrosion products at low temperatures.     

Determination of the Recoilless Fraction in Iron Oxide Nanoparticles Using the Two-lattice Method

We propose a two-lattice method for direct determination of the recoilless fraction using a single room-temperature transmission Mössbauer measurement. The method is first demonstrated for the case of iron and metallic glass two-foil system and is next generalized for the case of physical mixtures of two powders. We further apply this method to determine the recoilless fraction of hematite and magnetite particles. Finally, we provide direct measurement of the recoilless fraction in nanohematite and nanomagnetite with an average particle size of 19nm. A list of values obtained for the recoilless fraction in various materials using the two-lattice method is given.     

Method of Self-Mixing in the Spectroscopy of Quasielastically Scattered Laser Radiation

Interaction of a semiconductor laser with its self-radiation quasielastically scattered in the environment is considered. It is established that at small coefficients of coupling of the laser with the scattering medium the spectral density of the power of an optoelectronic signal in the laser faithfully reproduces the shape of the scattered-radiation spectrum at the Doppler-shift frequencies. This makes it possible to measure the spectrum with a resolution characteristic for optical homodynation by recording the optoelectronic signal.     

若干低维材料的拉曼光谱学研究--2004年度国家自然科学二等奖获奖项目介绍

文章扼要介绍了2004年国家自然科学二等奖获奖项目：《若干低维材料的拉曼光谱学研究》．用拉曼光谱研究低维纳米材料,必须对传统拉曼光谱学进行改造,创建新的“低维拉曼光谱学”．该项目通过若干低维材料的研究,为创建低维拉曼光谱学作出了系统的创新性贡献,如最先鉴认出典型低维材料的拉曼指纹谱,发现拉曼光谱的两个基本特征出现“反常”,但证明拉曼散射基本原理在低维体系中依然成立．通过低维拉曼光谱和光发射谱的应用研究,发现了材料的许多新奇物性,如发现超晶格和碳纳米管是类缺陷结构,和极性半导体纳米晶材料具有非晶特性,并提出了多孔硅的“量子限制电化学”形成和“多源量子阱”光发射模型,促进了低维材料和半导体器件的制备．     

环庚三烯酚酮稀土配合物的拉曼光谱研究

本文应用拉曼光谱研究了镧系金属镧 ,钕 ,钐和镱与环庚三烯酚酮配合物的配位方式及结构。研究结果表明 ,金属与环庚三烯酚酮配位后原对应于OH的伸缩振动谱峰消失 ,同时部分相关的谱峰频率也发生了明显的位移 ,在低波数 4 0 0 -5 0 0cm- 1区间检测到新的谱峰 ,并且该谱峰的位置随配合物中金属的不同而不同。根据拉曼光谱的研究结果推断了金属与配体的配位方式以及所得稀土金属配合物可能的结构。     

Near- and mid-infrared laser-optical sensors for gas analysis

Semiconductor diode lasers were first developed in the mid-1960s and found immediate application as much needed tunable sources for high-resolution laser spectroscopy commonly referred to as tunable diode laser absorption spectroscopy (TDLAS). In this paper, currently available semiconductor lasers for spectroscopy in the near- and mid-infrared spectral region based upon gallium arsenide, indium phosphite, antimonides and lead-salt containing compounds will be reviewed together with the main features of TDLAS. Room-temperature measurements of atmospheric carbon dioxide near 2 μm will be discussed and recent results obtained with a fast chemical sensor for methane flux measurements based on lead-salt diode lasers operating near 7.8 μm will be presented.     

Influence of vapor transport equilibration on Raman spectra of Er:LiNbO3 crystals

Raman spectra of as-grown and vapor transport equilibration (VTE) treated Er:LiNbO₃ crystals, which have different cut orientations (X-cut and Z-cut), different Er-doping levels (Er:(0.2, 0.4 and 2.0 mol%)LiNbO₃) and different VTE durations (80, 120, 150 and 180 h), were recorded at room temperature in the wavenumber range 50-1000 cm⁻¹ by using backward scattering geometry. The spectra were attributed on the basis of their spectral features and the previous experimental work and the most recent theoretical progress in lattice dynamics on pure LiNbO₃. In comparison with the pure crystal the most remarkable effect of Er-doping on the Raman spectrum is observed for the E(TO₉) mode. It does not appear at 610 cm⁻¹ as the pure crystal, but locates at 633 cm⁻¹. In addition, the doping also results in the lowering of the Raman phonon frequency, the broadening of the Raman linewidth and the changes of the relative Raman intensity of some peaks. The VTE treatment results in the narrowing of the linewidth, the recovery of the lowered phonon frequency and the further changes of relative Raman intensity. The narrowing of Raman linewidth indicates that the VTE processing has brought these crystals closer to stoichiometric composition. The VTE treatment has induced the formation of a precipitate ErNbO₄ in the high-doped Er(2.0%):LiNbO₃ crystals whether X- or Z-cut. For these precipitated crystals, besides above linewidth and phonon frequency features, they also display more significant Raman intensity changes compared with those not precipitated crystals. In addition, a slight mixing between A₁(TO) and E(TO) spectra is also observed for these precipitated crystals. Above doping and VTE effects on Raman spectra were quantitatively or qualitatively correlated with the characteristics of the crystal structure and phonon vibrational system.     

A high-pressure Raman and X-ray diffraction study of the perovskite SrCeO3

A high-pressure structural study of SrCeO₃ has been performed at room temperature by Raman spectroscopy and X-ray diffraction up to 32 and 45 GPa, respectively. A first-order reversible phase transition is observed at about 12 GPa in both techniques. A second weak structural change, taking place between 18 and 25 GPa, can be suspected from Raman data. The increase in the number of Raman bands and diffraction lines is an indication that the symmetry is lowered and the compound does not evolve towards the ideal cubic perovskite structure. A Rietveld analysis of X-ray data was performed for the low-pressure phase and the atomic positions and the cell lattice parameters variations are reported in this paper. The volume compressibility derived from Raman modes (5.6×10⁻¹² Pa⁻¹), involving mainly bond-stretching for each type of polyhedron, is found to be close to the one obtained from volume cell variations measured by X-ray diffraction (7.9×10⁻¹² Pa⁻¹).