Näherungsverfahren zur Auswertung von ESR-Spektren

In general the determination of the line-shape data of electron spin resonance of free radicals is only possible by using a computer. Therefore the superposition of Lorentzian is often replaced by a single over-all Lorentzian line. However, the disadvantage of this simplification is the impossibility to explain the variation of the line-shape factor. Formulae are given for the approximative determination of the line-shape data, which explain the variation of both the linewidth and the line-shape factor. To test the approximation, a comparison between the exact computed parameters of the tetracyanoethylene anion, given byGendell, Freed andFraenkel, and our calculation have been made.     

Line-shape of light absorption by excitons in one-, two- and three-dimensional molecular structures

Within the framework of the dipole approximation the line-shape of light absorption for exciton transitions between narrow bands in one-, two- and three-dimensional periodic structures are calculated. Exciton damping due to lattice imperfections is accounted for as a frequency independent parameter. The obtained analytical expressions allow analysis of the line-shape for different space dimensions of structure depending on bandwidth difference, damping and temperature.     

多模气体激光纵模线型函数及其频宽的实验观测

本文根据多模激光时间相干性ｇ（１）（τ）的准周期性特点，提出了一种观测多模激光纵模线型函数及其频宽的新方法－程差２ｋＬ法。文章介绍了测量原理与方法，并以双模Ｈｅ－Ｎｅ激光器为例，给出了相应的实验结果，研究表明，多模气体激光的纵模线型函数为洛仑兹（Ｌｏｒｅｎｔｚ）线型函数，相应的纵模频宽约为１０＾７Ｈｚ。     

Spectral line-shapes investigation with Pound-Drever-Hall-locked frequency-stabilized cavity ring-down spectroscopy

A review of recent experiments involving a newly developed Pound-Drever-Hall-locked frequency-stabilized cavity ring-down spectroscopy (PDH-locked FS-CRDS) system is presented. By comparison to standard FS-CRDS, the PDH lock of the probe laser to the ring-down cavity optimized coupling into the cavity, thus increasing the ring-down signal acquisition rate nearly 300-fold to 14 kHz and reducing the noise-equivalent absorption coefficient by more than an order of magnitude to 7 × 10^?11 cm^?1. We discuss how averaging approximately 1000 spectra yielded a signal-to-noise ratio of 220000. We also discuss how the spectrum frequency axis was linked to an optical frequency comb, thus enabling absolute frequency measurements of molecular optical transitions at sub-MHz levels. Applications of the spectrometer to molecular line-shape studies are also presented. For these investigations, we use semi-classical line-shape models that consider the influence of Dicke narrowing as well as the speed dependence of the pressure broadening and shifting to fit spectra. We show that the improved precision and spectrum fidelity of the spectrometer enable precise determinations of line-shape parameters. We also discuss the importance of line-shape analysis with regard to the development of new spectroscopic databases as well as in the optical determination of the Boltzmann constant.     

Temperature dependent phonon confinement in silicon nanostructures

Temperature dependent variation in Raman line-shape from silicon (Si) nanostructures (NSs) is studied here. Asymmetry and red-shift in room temperature Raman spectrum is attributed to phonon confinement effect. Raman spectra recorded at higher temperatures show increase in FWHM and decrease in asymmetry ratio with respect to its room temperature counterpart. Theoretical Raman line-shape analyses of temperature dependence of phonon confinement is done by incorporating the temperature dependence of phonon dispersion relation. Experimental and theoretical temperature dependent Raman spectra are in good agreement.     

密度矩阵理论在动态NMR中的应用

在交换影响可观测得到的温度范围内作定态全线型拟合是确定速率常数和活化参数的最佳方法。对弱偶合交换体系,理论线型可用改型的Bloch方程计算,但强偶合体系就需作全密度矩阵处理。本文的目的是说明如何用密度矩阵方法计算线型。内容包括密度矩阵的基本理论,以及密度矩阵理论在分子内和分子间交换体系的NMR线型计算中的应用。     

Line-shape parameters in infrared bands of sulfur dioxide

This paper presents the calculated results for line-shape parameters in the v₁ and v₃ bands of sulfur dioxide for temperatures between 300 and 1200°K, together with the self-broadening coefficients for some particular rotational lines. The Anderson-Tsao-Curnutte theory was applied to calculate the line half-widths, and a criterion was introduced to determine the line-shape parameters on the basis of a narrow-band model. The calculated results are greatly different from previously assumed values.     

Optical line-shape and the time-domain photon echo measurement in semiconductor quantum dots

It is shown theoretically that, because of the characteristic line-shape of the electronic spectral density, the experimental photon-echo signal, giving the dephasing of the electronic state of a quantum dot, should be modulated in time quasi-periodically. This suggestion is demonstrated numerically for the case of InAs quantum dots for several temperatures of the sample. A comparison with the recent experiments on CdSe nanocrystals is presented. The theoretical argumentation is based on the recent theoretical calculation of the homogeneous optical line-shape based on the multiple electron–LO–phonon scattering in quantum dots.     

Effects of Double Modulation on Electrically Detected Magnetic Resonance Signal Intensity and Lineshape

The effects of external magnetic-field modulation as well as microwave-power modulation on the signal intensity and line-shape are considered for an electrically detected magnetic resonance signal. It is shown that the signal increases in amplitude and then splits into two lines with increasing magnetic-field-modulation amplitude. A theory is developed which fits the experimental results extremely well and it is concluded that the double modulation can be used to obtain information about component lines as well as to enhance signal-to-noise.     

Stochastic aspects in the theory of spectral-line broadening. II. Noncommutative cluster expansions

Generalizing ideas of von Waldenfels we develop a systematic procedure to define truncatedn-point operators which are reminiscent of Ursell functions of statistical mechanics. The truncation procedure is adapted to factorization relations obeyed by the operators in question. The results are applied to spectral-line broadening in plasmas. We derive cluster expansions for the line-shape function in terms of these truncated operators, where the ions are treated quasistatistically. The first order approximation for the line-shape function is discussed. The results are carried over to several moving perturber species, in particular to nonquasistatic ions.     

Doublet luminescence due to coexistence of excitons and electron-hole plasmas in optically excited CH3NH3PbBr3 single crystal

Doublet luminescence from hybrid metal trihalide perovskite semiconductors is observed along with materials processing when high-quality single crystals are obtainable. Yet, the underlying physical mechanism remains poorly understood. Here, we report controllable solution-processed crystallization that affords high-quality CH₃NH₃PbBr₃ single crystals with atomically flat pristine surfaces. Front-face photoluminescence (PL) shows doublet luminescence components with variable relative intensities depending on the crystal surface conditions. We further find that the low-energy PL component with asymmetric spectral line-shape becomes predominant when the atomically flat crystal surfaces are passivated in the ion-abundant saturated solutions, while poor-quality single crystal with visually rough surface only gives the high-energy PL with symmetric line-shape. The asymmetric spectral line-shape of the low-energy PL matches perfectly with the simulated bandedge emission. Therefore, the low-energy PL component is attributable to the intrinsic bandedge emission from the crystal bulk while the high-energy one to surface-specific emission. Elliott fitting to the absorption data and multi-exponential fitting to the time-resolved photoluminescence traces jointly indicate the coexistence of excitons and electron-hole plasmas in optically excited CH₃NH₃PbBr₃ single crystals, thereby catching the physical merit that leads to the occurrence of doublet luminescence.     

A new calculation for line broadening of Lyman-α in plasmas

A line-shape calculation of Ly-α is presented which uses a new method based on operator-valued temporal correlation functions.     

基于光梳的腔增强傅里叶变换光谱：在碰撞线形研究中的应用

本文在近红外区域构造了基于光学频率梳的腔增强傅里叶变换光谱仪，并用于Ar干扰的CO振转跃迁的谱线研究，高灵敏度的测量波数从6270 cm^-1到6410 cm^-1，涵盖CO第二泛频带的P和R分支. 该光谱仪提供的高分辨率超过了由干涉图长度确定的傅立叶变换分辨率极限，成功消除了线型函数的振铃和展宽效应. 本文可观察到Voigt线型曲线外的碰撞效应. 通过拟合速度依赖的Voigt曲线重新得到碰撞线型曲线参数，并与使用基于光学频率梳的高精密连续激光光腔衰荡光谱测量结果非常吻合.     

On the precision of calculations of initial state radiation in the LEP Z line-shape fits

Calculation of initial state radiation (ISR) in the fitting program MIZA and in the Standard Model program BHM is improved within the analysis of the Z line-shape measurements at LEP. The uncertainty on the determination of the Z line-shape parameters coming from the precision of ISR calculations is 2×10⁻⁴ on σ₀ and 0.1 MeV on m_Z and Γ_Z.     

Chemical states of dodecanethiolate-passivated Au nanoparticles: synchrotron-radiation photoelectron spectroscopy

We have carried out a photoemission study using synchrotron radiation of dodecanethiolate (DT)-passivated Au nanoparticles supported on the highly oriented pyrolytic graphite substrates. From detailed line-shape analyses of Au 4f core-level photoemission spectra of DT-passivated Au nanoparticles, it was found that Au 4f core-level spectra consist of two components. We attribute these components to the inner Au atoms and surface Au atoms bonded to surface dodecanethiolates. From these results, we discuss the chemical states of the present DT-passivated Au nanoparticles.     

Hilbert transforms of resonance functions

Expressions have been derived for the Hilbert transforms of resonance functions for induction and dispersion forces in spectral line-shape theories. These functions are evaluated numerically and are also represented by power series.     

Photoelectron and Penning ionization electron spectrometry with a differential retarding field analyzer

A differential retarding field analyzer of the type described by Lindau et al.² has been tested in detail by photoelectron spectrometry in the 0–10-eV range. A resolution of 17 meV was obtained together with a satisfactory line-shape and sensitivity. The important potential parameters concerning resolution and line-shape, and the energy-dependence of the transmission of the analyzer have been determined experimentally. As a first application, Penning ionization electron spectra for the systems He(2³S)-N₂ O₂, and HCl have been obtained with the transmission-calibrated analyzer.     

A study of the dynamic equilibrium between symmetrical and distorted 1,2,3-trimethylcyclohexane radical cations

Radical cations of the 1,2,3-trimethylcyclohexane isomers stabilized in various γ-irradiated solute/halocarbon matrices have been investigated by means of ESR in the temperature range 4–77K. At 4 K the ESR spectra are dominated by contributions from an asymmetrically distorted structure with the unpaired electron localized to the C1-C2 bond. On increasing the temperature a reversible change occurs in the ESR line-shape of the cations of the two symmetrical isomers. Using a two-site jump model to reproduce the temperature dependent line-shape, the phenomenon is explained in terms of an interconversion between two such distorted structures, each being the mirror image of the other. The Arrhenius plot associated with the process is markedly nonlinear towards the low temperature region. The experimental data are also modelled by postulating that another (different) electronic ground state, having higher symmetry, becomes populated with the increase of temperature. In this way, the spectral changes can be simulated using a three-site jump model which couple the thermally activated two-site jump process (E _a ca. 0.137 kcal/mol) with a dynamical equilibrium between the asymmetrical ground state and a symmetrical structure 0.058 kcal/mol higher in energy. The energy barrier to pass from the distorted to the symmetrical structure was evaluated to be 0.085 kcal/mol.     

拉曼光谱研究n型4H-和6H-SiC晶体的载流子浓度

半导体材料的纵光学声子与等离子体激元耦合模(LOPC模)能够提供材料电学方面的相关信息。本文在室温下测得了n型4H-和6H-SiC的拉曼光谱,分析了掺入的杂质对于SiC晶体拉曼光谱的影响,通过拟合n型4H-和6H-SiC晶体的LOPC模的线型得到等离子体频率,并由此从理论上计算了载流子浓度。载流子浓度的理论计算值与霍尔测量的结果符合得很好。研究结果进一步证实了对于n型4H-和6H-SiC晶体,可以通过分析LOPC模的线形来较准确地给出相关材料的载流子浓度。