Books received

The inhomogeneous broadening of optical transitions in solids is of fundamental importance in understanding the interaction of optical centres with their environment. In perfect crystals optical linewidths are determined by excited state lifetime and other d-phasing mechanisms such as the electron-phonon interaction. However, in real crystals random differences of impurities in crystallographically equivalent sites result in overlapping transitions and inhomogeneously broadened Gaussian lines. The suppression of inhomogeneous broadening of solid-state spectra using optical hole-burning and fluorescence line-narrowing techniques is discussed in terms of the determination of the homogeneous widths, multi-site geometries and the distributions of spectroscopic parameters that accompany disorder in a number of laser crystals and glasses.     

Absorption and photoluminescence studies of the temperature dependence of exciton life time in lattice-matched and strained quantum well systems

We present systematic studies of the temperature dependence of linewidths and lifetimes of excitonic transitions in quantum wells grown by molecular beam epitaxy using both photoluminescence(PL) and optical absorption. The temperature ranged from 6K to room temperature. Samples under investigation were lattice-matched GaAs/AlGaAs and InGaAs/InAlAs, and strained InGaAs/GaAs and InGaAs/AlGaAs quantum wellssystems. In addition, the effects of well-size variations in GaAs/AlGaAs quantum wells were measured and analyzed. In all cases we were able to observe the excitonic transitions up to room temperature. By a careful fitting of the experimental data we separated the exciton transitions from band-to-band transitions. By deconvoluting the excitonic transitions we obtained the homogeneous and inhomogeneous linewidths. The homogeneous linewidths were used to calculate the exciton lifetimes as a function of temperature using the Heisenberg uncertainty principle. We found the lifetime decreases significantly with temperature and increases with increasing well size. These results are interpreted in terms of the exciton-phonon interaction and are expected to be very useful for the design of semiconductor optical devices operating at different temperatures.     

Magic-angle-spinning NMR on solid biological systems. Analysis Of the origin of the spectral linewidths

Magic-angle-spinning (MAS) high-power ¹H-decoupled ¹³C and ³¹P NMR has been applied to solid biological materials to obtain information about the mechanisms that determine the spectral linewidths. The line broadening in MAS ³¹P NMR spectra of solid tobacco mosaic virus (TMV) has been investigated by selective saturation and T₂ measurements. About 90 Hz stems from homogeneous effects, whereas the inhomogeneous contribution is approximately 100 Hz. The inhomogeneous line broadening is assigned to macroscopic inhomogeneities in the sample and not to variations in the nucleotide bases along the RNA strand in TMV. It is concluded that sample preparation is of vital importance for obtaining well-resolved spectra. Under optimal preparation techniques the isotropic values of the chemical shift of the different ³¹P sites have been determined to obtain information about the secondary structure of the viral RNA. The chemical shift anisotropy has been determined from the relative intensities of the spinning side bands in the spectra. The chemical shift information is used to make a tentative assignment of the resonance in terms of the three structurally distinguishable phosphate groups in TMV. The origin of the linewidths in MAS NMR has been examined further by ¹³C NMR of approximately 10% ¹³C-enriched coat protein of cowpea chlorotic mottle virus, using selective excitation and saturation techniques, as well as measurements of the relaxation times T_1γ and T₂. The CO resonance in the spectrum is composed of an inhomogeneous and homogeneous part with a total linewidth of 700 Hz. The homogeneous linewidth, contributing with 200 Hz, is found to arise from slow molecular motions in the solid on a millisecond timescale.     

Extremely slow charge fluctuations in the metallic state of the two-dimensional molecular conductor theta-(BEDT-TTF)2RbZn(SCN)4

Large charge disproportionation has been confirmed in the metallic state of a 1/4-filled organic conductor theta-(BEDT-TTF)2RbZn(SCN)4 by means of 13C-NMR analysis on a selectively 13C-enriched single crystal sample. By comparing the homogeneous and inhomogeneous linewidths, the temperature dependence of the extremely slow dynamics of charge fluctuations has been determined first. The exotic nature of the metallic state of this salt is discussed.     

Raman scattering in GeSi alloys

Room temperature Raman spectra are reported for polycrystalline GeSi alloys as a function of composition. The frequencies and linewidths of the three main peaks show some disagreement with previously reported work; the results are discussed within the theories of local and resonance modes of impurities, where possible. Minor scattering peaks and second-order spectra, as well as anomalous behavior in several inhomogeneous samples, are also reported and discussed.     

Spectral-luminescent properties and photoinduced transformations of bisanthene and bisanthenequinone

Based on the study of photochemical transformations of bisanthene in oxygen-containing solutions, it was established that the final product of this reaction is bisanthenequinone. It is shown that in the course of this oxidation reaction the intermediate compounds endomonoperoxide and bisanthene endobiperoxide are formed. Quantum-chemical calculation of the geometrical structure and electronic spectra of the endoperoxides has shown that they have a nonplanar structure, and their absorption spectra experience a large hypsochromic shift. The absorption and fluorescence spectra of solutions of bisanthene in different solvents at 300 and 77 K were investigated. The large Stokes shift of the fluorescence spectra of the solutions of bisanthene in benzene and in its methyl derivatives is explained by the action of intermolecular interactions. The quasi-line fluorescence spectra of solutions of bisanthene in the matrices of saturated hydrocarbons were recorded. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 2, pp. 176–182, March–April, 2000.     

Spectroscopy inside the homogeneous linewidth in three-coupled level system

Features narrower than the two-levels homogeneous linewidths can occur in laser-saturation spectroscopy experiments on three levels systems. They are described and demonstrated on vibrational-rotational molecular spectra.     

Spectroscopy of polymorphic forms of Mg phthalocyanine

Some specific features of the absorption, luminescence, and internal photoelectric effect spectra of nanocrystals of Mg phthalocyanine of the β and X aggregate forms obtained by crystallization from molecular solutions of Mg phthalocyanine are revealed and studied. The complex structure of the spectra of the crystalline forms is attributed to the simultaneous presence of both crystalline phases and the molecular phase of Mg phthalocyanine in the samples. Comparison of the absorption and luminescence spectra is an effective diagnostic tool for optimization of the methods of preparation of single-phase Mg-phthalocyanine objects. Similar results were also observed in the spectroscopic study of other metal phthalocyanine derivatives.     

Low temperature laser fluorescence and excitation spectra of free base phthalocyanine in normal alkanes matrices (Shpolskii effect)

Excitation and fluorescence spectra of free base phthalocyanine were studied in matrices of normal alkanes (C₈H₁₈, C₁₂H₂₆, C₁₆H₃₄) at low temperatures (5 to 30 K). Narrow band excitation of fluorescence using a pulsed tunable dye laser was used for site selection to eliminate ambiguities due to impurities and multiple sites. Fluorescence and excitation spectra show quasiline structure. Multiplicity of 0-0 transitions depends on the chain length of normal alkanes. The spectra and frequencies of normal vibrations are compared with those of phthalocyanine in other n-alkanes (C₉H₂₀, C₁₀H₂₂) and noble gas matrices (Ar, Ne) under different excitation conditions.     

Laser induced fluorescence line narrowing in iodine

A complementary technique to Lamb dip absorption spectroscopy in gases is described which allows observation of homogeneous linewidths in fluorescence. Hyperline spectra of iodine excited by a single mode argon laser beam at 5145 Å are presented for the 43-13 and 43-11 bands at 5970 and 5830 Å respectively.     

Photochemistry of tetrasulphonated magnesium phthalocyanine in water and DMSO solutions by Raman, femtosecond transient absorption, and stationary absorption spectroscopies

Photochemical and photophysical behavior of the tetrasulphonated magnesium phthalocyanine MgPcS₄ has been studied by Raman spectroscopy, femtosecond transient absorption, and stationary UV–VIS absorption spectroscopies. It has been shown also that the dimerization equilibrium constant K for the tetrasulfonated magnesium phthalocyanine is strongly shifted towards monomeric form in DMSO solutions compared to aqueous systems. The Raman and emission spectra recorded in the range of 294–77 K combined with the femtosecond transient absorption reveal spectral features that provide unique information about the primary photochemical and photophysical events of magnesium phthalocyanines in liquid solutions as well as in the crystal frozen matrices.     

国内CIDEP研究进展

化学诱导动态电子极化（CIDEP）是检测瞬态顺磁粒子并表征其特征的强有力的手段,对于研究光化学和光物理瞬态过程的微观机理和规律有重要意义. 本文较为详细地总结了4种常见的CIDEP机理,讨论了各种极化谱及相应的极化条件;简要介绍了国内研究小组在CIDEP理论以及在均相溶液和微复相体系中光化学过程的CIDEP研究成果.      

新型酞菁的光致发光性质研究

研究了2,3-四-(2-异丙基一5-甲基苯氧基)氢酞菁在10,77,177和300 K下石英衬底上的浇铸膜和单晶硅衬底上真空镀膜(约200 nm厚)在300 K下光致发光光谱.氢酞菁的浇铸膜光致发光光谱在上述温度下均出现荧光发射和磷光发射峰,在177和300 K下出现了1 673 nm激基缔合物峰.该峰的出现与分子抗聚集能力的强弱有关,在300 K激基缔合物峰比在177 K下的峰强,从氢酞菁分子结构特点讨论了形成激基缔合物的原因.随着温度的升高,可以观察到荧光发射峰渐渐减弱而激基缔合物峰变强.由于浇铸膜和真空镀膜的酞菁分子聚集态不同导致了斯托克司位移的差异,真空镀膜的发光峰峰值在1 140 nm左右,与酞菁浇铸膜的峰值差别较大.浇铸膜的发光峰的半高宽为300 nm,而真空镀膜发光峰的半高宽为100 nm左右.     

四氯苯醌与嘧啶类核酸碱基的光化学氢抽取和电子转移反应

采用纳秒时间分辨的激光闪光光解实验技术,研究了四氯苯醌(TCBQ)分子与两种嘧啶核酸碱基(胸腺嘧啶和尿嘧啶)分子在355nm激发下的光化学反应动力学. 355 nm将TCBQ分子布居到激发三重态³TCBQ^*,高反应活性的³TCBQ^*与碱基分子发生两个平行的反应,氢抽取反应和电子转移反应,分别对应生成瞬态光谱上观测到的两个光反应产物TCBQH·和TCBQ·^-. 这两个反应同时生成的碱基自由基和碱基阳     

Homogeneous and inhomogeneous magnetic oxide semiconductors

Magnetic oxide semiconductors are significant spintronics materials.In this article, we review recent advances for homogeneous and inhomogeneous magnetic oxide semiconductors.In the homogeneous magnetic oxide semiconductors,we focus on the various doping techniques including choosing different transition metals, codoping, non-magnetic doping,and even un-doping to realize homogeneous substitution and the clear magnetic origin.And the enhancement of the ferromagnetism is achieved by nanodot arrays engineering, which is accompanied by the tunable optical properties.In the inhomogeneous magnetic oxide semiconductors, we review some heterostructures and their magnetic and transport properties, especially magnetoresistance, which are dramatically modulated by electric field in the constructed devices.And the related mechanisms are discussed in details.Finally, we provide an overview and possible potential applications of magnetic oxide semiconductors.     

取代基对稀土夹心双酞菁铥荧光特性的影响

利用稳态荧光和时间分辨荧光方法研究了三明治型酞菁铥的荧光特性及其浓度、激发波长和取代基对荧光特性的影响。实验发现:3种双酞菁铥的氯仿溶液在700 nm处具有较强的荧光发射,给电子基-OC₈H₁₇的加入使得酞菁大环上π电子的离域性增强,降低了π分子轨道的能级差;同时,烷氧基上非成键电子能够和共轭体系中的π电子相互作用,形成p-π共轭,进一步降低了π-π^*之间的能级差,从而使荧光谱中发射峰的峰位发生红移,峰的强度也有变化。3种酞菁铥化合物在700 nm左右的荧光具有两个寿命,分别为单体和聚集体产生的,随着浓度的降低,单体成分逐渐增多。     

Low-temperature absorption and fluorescence spectra of phthalocyanine in n-alcanes and in polyethylene (Shpolskii's effect)

Absorption and fluorescence spectra of free base phthalocyanine were studied in matrices of n-alcanes (C₈H₁₈, C₁₂H₂₆, C₁₆H₃₄) and polyethylene at 77 K and 4·2 K. The spectra show quasi-line structure whose multiplicity increases with increasing number of carbon atoms of the solvent and decreasing temperature. In the low-temperature spectra of phthalocyanine in polyethylene films only band spectra have been observed.I wish to thank Prof. DrSc K.Vacek, Head of The Department of Chemical Physics, Charles University for stimulating discussions.     

A closer look at photochemical reactions of transition-metal compounds by time-resolved EPR

A review is given of applications of time-resolved electron paramagnetic resonance (TREPR) in the field of photochemistry of transition-metal compounds. The two main TREPR techniques used in these studies are described. A brief overview is given of chemically induced dynamic electron polarization mechanisms that can affect TREPR spectra and that can give insights into the mechanism of photochemical reactions. Following these background sections, experimental results are presented. The discussion focuses in particular on the Fourier-transform EPR studies of photoinduced metal-alkyl bond homolysis reactions of a series of transition-metal (Co, Ru, Re, Pt) complexes carried out by the authors.     

水溶性酞菁类光敏剂的合成及其光谱性质研究

以3-硝基邻苯二甲腈与3-巯基-1-丙磺酸钠为原料,在醋酸盐存在下通过四环化合成了三种带四个3-磺基丙基磺酰基的水溶性酞菁。利用紫外-可见吸收光谱,荧光光谱等对其光谱性质进行了测量,并计算了其荧光量子产率和单线态氧量子产率。引入吸电子基团所合成的水溶性酞菁与ZnPc相比,其荧光发射光谱的形状并未改变,但其最大荧光发射波长均发生10 nm以上的红移。三种水溶性酞菁中锌酞菁的荧光量子产率最高,铜酞菁的荧光量子产率最低;它们在水溶液中的荧光呈双指数衰减,这可归结为激发态质子化或去质子化的结果。单线态氧量子产率锌酞菁最大,空心酞菁次之,铜酞菁最小。光谱分析结果表明,合成的锌酞菁和空心酞菁具有高的单线态氧量子产率和高的光稳定性,有望用作光动力治疗和光免疫治疗的光敏剂。     

Mössbauer Spectroscopy of Locally Inhomogeneous Systems

The paper considers ways for obtaining information from Mössbauer spectra of locally inhomogeneous systems. The entire notion locally inhomogeneous system (LIS) is given a more precise definition applied to Mössbauer spectroscopy. There are considered factors that lead to local inhomogeneity of hyperfine interactions and its mechanisms. Application of LIS Mössbauer spectra processing and analysis methods are discussed. Ways for comprehensive utilization of various methods are described along with the role of a priori information at all processing stages.