近红外光谱分析中的高斯过程回归方法

将高斯过程算法引入化学计量学领域,用于挖掘近红外光谱与被测物组分之间的复杂关系.为增加模型的稳健性,首先采用了蒙特卡罗交叉验证方法以去除异常样本,而后多元散射校正、平滑、导数等方法被用于模型的预处理.近红外光谱在经过无信息变量去除算法处理后,在保留有用信息的基础上大大缩减了波长点数,以这些特征波长点作为输入建立的分析模型更具有解释能力和稳健性.为验证算法的有效性,使用了一组公开的数据集,它包含了80个玉米样品的近红外光谱以及油、淀粉、蛋白质的含量值.GP回归算法被用于分析这三种组分的含量,所得模型的评价指标分别采用校正、校正集交叉验证均方根误差、预测均方根误差以及各自的相关系数.结果显示,模型的校正相关系数r达到0.99以上,预测时的相关系数r也在0.96以上,验证了该算法的有效性.     

Determination of thiophanate-methyl using UV absorption spectra based on multiple linear regression

As one worldwide used agent for fungi control in the fruit and vegetable field, thiophanate-methyl has been constituted a significant health risk. To determinate thiophanate-methyl, the method using UV absorption spectra based on multiple liner regression is used. Principal absorption wavelengths related closely with thiophanate-methyl ethanol solution are confirmed through analyzing the absorption spectra of thiophanate-methyl. Utilizing multiple linear regression, mathematical model between absorbance obtained from fourteen absorption wavelengths and thiophanate-methyl concentration is established. The result shows concentrations between the predicted values and measured values are well coincident and the related coefficient is 0.9853 over the concentration range 2–35 ppm.     

PLE spectra analysis of the sub-structure in the absorption spectra of CdSeS quantum dots

The semiconductor CdSeS quantum dots (QDs) embedded in glass are analysed by means of absorption spectra, photoluminescence (PL) spectra and photoluminescence excitation (PLE) spectra. The peaks of absorption spectra shift to lower energies with the size of QD increasing, which obviously shows a quantum-size effect. Using the PLE spectra, the physical origin of the lowest absorption peak is analysed. In PLE spectra, the lowest absorption peak can be deconvoluted into two peaks that stem from the transitions of 1S_3/2--1S_e and 2S_3/2--1S_e respectively. The measured energy difference between the two peaks is found to decrease with the size of QD increasing, which agrees well with the theoretical calculation for the two transitions. The luminescence peak of defect states is also analysed by PLE spectra. Two transitions are present in the PLE, which indicates that the transitions of 1S_3/2--1S_e and 2S_3/2--1S_e are responsible for the defect states luminescence.     

Modeling variations in near-infrared spectra caused by the coherent backscattering effect

We study a new optical effect, a spectral manifestation of coherent backscattering, which reveals itself as systematic variations in the depth of absorption bands with changing phase angle. We used Cassini VIMS near-infrared spectra of Saturn's icy satellite Rhea in order to identify and characterize the spectral change with phase angle, focusing on the change in the depth of water-ice absorption bands. To model realistic characteristics of the surfaces of icy satellites, which are most likely covered by micron-sized densely packed particles, we perform simulations using a theoretical approach based on direct computer solutions of the macroscopic Maxwell equations. Our results show that this approach can reproduce the observed phase-angle variations in the depth of the absorption bands. The modeled changes in the absorption bands are strongly affected by physical properties of the regolith, especially by the size and packing density of the ice particles. Thus, the phase-angle spectral variations demonstrate a promising remote-sensing capability for studying properties of the surfaces of icy bodies and other objects that exhibit a strong coherent backscattering effect.     

Resolution of interatomic distances by fourier analysis of short energy-range X-ray absorption spectra

Based on the example of signals with a known form of functional dependence, as is the case in X-ray absorption spectroscopy (XAS), the applicability of the available general estimates of the frequency resolution limits in the case of determining two close interatomic distances by a Fourier analysis of short energy range XAS spectra is considered. A method for the Fourier analysis of such spectra over a small interval of photoelectron wavenumbers, ～3–4 Å^?1, is proposed. The method is applied to the K-XAS spectra of As calculated for different pressure-induced distortions of the nearest environment of the As atom in an InAs crystal. This made it possible to identify an adequate model for the radial distribution of coordinating In atoms among alternative models and, based on this model, to resolve two As-In distances that differ by 0.03 Å. A Fourier analysis of the experimental As K-XAS spectrum of an InAs crystal subjected to a pressure of 11 GPa performed based on this method made it possible to determine the character of distortions of the nearest environment of the As atom under this pressure; namely, it was found that the radial distribution of the six coordinating In atoms corresponds to the (1 + 4 + 1) model. For this distortion model, the As-In interatomic distances were determined.     

Measurements of X-ray absorption spectra by the prism spectroscopy method

X-ray absorption spectra of a number of samples were measured in the range 5–30 keV by the prism spectrophotometry method. The spectral decomposition was performed using an optically polished diamond prism with an opening angle of 90°. The absorption spectra of liquid bromonaphthalene are presented as an example. An energy resolution of 100–130 eV was achieved in the energy range of ～10 keV, providing the unambiguous identification of elements by jumps in the K photoabsorption.     

Enhanced light absorption of silicon in the near-infrared band by designed gold nanostructures

A scheme to enhance near-infrared band absorption of a Si nanoparticle by placing the Si nanoparticle into a designed gold nanostructure is proposed. Three-dimensional （3D） finite-difference time-domain simulations are employed to calcu- late the absorption spectrum of the Si nanostructure and maximize it by generating alternate designs. The results show that in the near-infrared region over 700 nm, the absorption of a pure Si nanoparticle is very low, but when the same nanoparticle is placed within an optimally designed gold nanostructure, its absorption cross section can be enhanced by more than two orders of magnitude in the near-infrared band.     

Fermi-level engineering of BaTiO3 by alkali codoping: increasing the near-infrared absorption by rhodium

Using electron paramagnetic resonance, optical absorption, and fast spectroscopy of light-induced absorption changes, it is shown that codoping BaTiO₃:Rh with Na_Ba acceptors raises the charge state of Rh³⁺ to Rh⁴⁺. Subsequent oxidation under high oxygen pressures can lower the Fermi level to Rh^4+/5+, leading to increased infrared absorption. The light-induced charge transfer in such specimens is characterised by “one center” behaviour. Received: 18 November 1998 / Revised version: 23 December 1998 / Published online: 7 April 1999     

香荆芥酚的荧光光谱和吸收光谱研究

研究了中药活性成分香荆芥酚(Carvacrol)的荧光光谱和吸收光谱,依据光谱数据测量了香荆芥酚的电离常数和荧光量子产率.在pH＜2.0时,香荆芥酚的荧光随溶液pH增大而增强;在pH2.0～8.0范围内,香荆芥酚有稳定的强荧光,最大激发波长为278 nm,最大发射波长为306 nm; pH＞8.0时荧光强度随pH的增大...     

Measurements of absorption spectra of thin films by the waveguide technique

The waveguide technique for measuring the absorption spectra of thin films in spectral range of their transparency is considered. The error of measuring the absorption of a ～0.1 μm thick film does not exceed 5% at an absorption coefficient of less than 50 cm^–1. Capabilities and limitations of the method are discussed.     

Polarization measurement and configuration analysis of the triplet-triplet absorption spectra of substituted naphthalenes

The polarization of triplet-triplet absorption spectra for 1- and 2-methoxynaphthalene, 1,5-, 1,8-, 2,7-, and 2,3-naphthalenediols, and 1,4-dimethoxynaphthalene was measured by the photoselection method. Calculations of the triplet states of these molecules were made by the Pariser-Parr-Pople method, and the resulting wavefunctions were subjected to the configuration analysis. The T-T absorption spectra of the β-substituted naphthalenes are relatively simple and closely resemble that of naphthalene. In the α-substituted naphthalenes, the T-T absorption spectra are not only remarkably different from that of naphthalene but also different from one another. Comparison of experimental and theoretical results leads to reasonable assignments of the individual absorption bands involving some modification of previous assignments. The apparent complexity of T-T absorption spectra of the α-substituted naphthalenes can be interpreted in relation to the enhanced and transitions of naphthalene.     

Theoretical analysis of the experimental UV-Vis absorption spectra of some phenolic Schiff bases

The time-dependent density functional theory (TDDFT) was applied in conjunction with the natural bond orbital analysis to examine the UV-Vis properties of 10 phenolic Schiff bases. The calculations were performed with different functionals, but main discussion refers to results obtained at the B3LYP/6-311+G(d,p) level of theory. The approach based on the natural localised molecular orbital clusters indicates similar behaviour for majority of examined compounds. The HOMO (“highest occupied molecular orbital”) cluster is delocalised over the ring which is electron richer, the HOMO-1 cluster is spread over the other ring, whereas the LUMO (“lowest unoccupied molecular orbital”) cluster is situated on the imino group. The two bands at long wavelengths correspond to the HOMO → LUMO and HOMO-1 → LUMO transitions, i.e. from both A and B rings to the imino group. The next band originates from a transition from the imino group to the imino group. The band at the smallest wavelengths originates from a transition from the A ring to the A ring, or from the B ring to the B ring. Our findings are in very good agreement with the existing literature data.     

等离子体X射线吸收谱及发射谱研究

 报道计算高温高密等离子体吸收谱和发射谱（光学薄）的理论方法；该方法基于相对论原子理论，可以计算任何单元素以及多元素等离子体的谱分辨X射线吸收谱和发射谱（光学薄）；应用了量子亏损理论，可以减少计算量。利用该方法计算金等离子体LTE吸收谱，计算结果与实验符合良好。本文还对金等离子体LTE的光学薄发射谱进行了研究, 这将有利于对实验进行进一步的诊断分析。该理论计算方法还可提供等离子体内各电离度能级布居等重要物理参数。因此经“标准实验”检验的该理论计算方法将是提供ICF“精密”物理辐射参数的重要基础。     

等离子体X射线吸收谱及发射谱研究

报道计算高温高密等离子体吸收谱和发射谱（光学薄）的理论方法;该方法基于相对论原子理论,可以计算任何单元素以及多元素等离子体的谱分辨X射线吸收谱和发射谱（光学薄）;应用了量子亏损理论,可以减少计算量。利用该方法计算金等离子体LTE吸收谱,计算结果与实验符合良好。本文还对金等离子体LTE的光学薄发射谱进行了研究, 这将有利于对实验进行进一步的诊断分析。该理论计算方法还可提供等离子体内各电离度能级布居等重要物理参数。因此经“标准实验”检验的该理论计算方法将是提供ICF“精密”物理辐射参数的重要基础。