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991.
In this minireview, modern multifrequency electron paramagnetic resonance (EPR) spectroscopy, in particular, at high magnetic fields, is shown to provide detailed information about structure, motional dynamics and spin chemistry of transient radicals and radical pairs occurring in photochemical reactions. Examples discussed comprise spin-polarized radicals and radical pairs in disordered systems, such as ultraviolet-irradiated quinone and ketone compounds in fluid alcohol solutions, green-light initiated electron transfer in biomimetic porphyrin?Cquinone donor?Cacceptor model systems in frozen solution, aiming at artificial photosynthesis, and red-light initiated electron transfer in natural photosynthetic reaction-center protein complexes. The transient paramagnetic states exhibit characteristic electron polarization (CIDEP) effects originating from a triplet mechanism, a radical-pair mechanism or a correlated coupled radical-pair mechanism. They contain valuable information about structure and dynamics of the short-lived reaction intermediates. Moreover, the CIDEP effects can be exploited for signal enhancement. Continuous-wave and pulsed versions of time-resolved high-field EPR spectroscopy, such as transient EPR and electron spin-echo experiments, are compared with respect to their advantages and limitations for the specific photoreaction under study. Furthermore, orientation resolving W-band pulsed electron-electron double resonance (PELDOR) experiments on the spin-correlated coupled radical pair $ {\text{P}}_{865}^{ \cdot + } $ $ {\text{Q}}_{\text{A}}^{ \cdot - } $ in frozen solution reaction centers from the purple photosynthetic bacterium Rb. sphaeroides reveal details of distance and orientation of the pair partners in their charge-separated transient state. The results are compared with those of the ground-state P865QA. In conjunction with Q-band proton electron-nuclear double resonance (ENDOR) experiments the W-band PELDOR results provide decisive evidence that the local structure of the QA binding site does not change under photoreduction of the quinone??in agreement with earlier FTIR studies. The examples given demonstrate that multifrequency EPR experiments on disordered systems add heavily to the capabilities of ??classical?? spectroscopic and diffraction techniques for determining structure?Cdynamics?Cfunction relations of biochemical processes, since short-lived intermediates can be observed in real time while staying in their working states at biologically relevant time scales. 相似文献
992.
以单个磁性中心的NiO以及由Co和Ni等元素构成的双磁性中心的纳米结构为例,总结了近年所做的主要工作.为了在理论上实现磁性纳米结构中的超快自旋翻转和转移,提出了一种称为Λ进程(Λ process)的超快自旋转换机理.在实际计算中,首先采用量子化学第一性原理计算得到磁性纳米结构中精确的隙间d电子态,然后考虑外加磁场和自旋轨道耦合分析磁性原子中的自旋局域化程度,最后引入激光脉冲项,研究在其作用下材料的自旋态经由Λ进程实现转换的时间历程.研究结果表明自旋翻转和转移可以在线偏振光的作用下在亚皮秒的时间尺度内完成.
关键词:
超快自旋动力学
第一性原理计算
Λ进程
磁性纳米结构 相似文献
993.
Christos Argirusis Francois JomardStefan F. Wagner Wolfgang MenesklouEllen Ivers-Tiffée 《Solid State Ionics》2011,192(1):9-11
For applications in high temperature fast conductometric gas sensors and oxygen membranes, several mixed conductors show promising features. In particular, acceptor-doped strontium titanate (STO) has been widely investigated for an application as a fast conductometric oxygen sensor. By a B-site substitution with 35% iron, the resulting ceramic solid solution SrTi0.65Fe0.35O3 (STF35) exhibits a temperature-independent conductivity, an ideal prerequisite for a gas sensor.In the presented study, the oxygen tracer exchange behavior and the tracer diffusion of dense ceramic STF35 bulks have been investigated in the temperature range between 600 and 900 °C by means of 18O2 tracer exchange experiments and subsequent secondary ion mass spectrometry (SIMS), resulting in the determination of k* and D* values, respectively.Furthermore, by coating the samples with a thin alkaline earth metal oxide layer (CaO), a significantly enhanced oxygen surface exchange reaction was observed. These findings are in good agreement with previous results on STO single crystals. 相似文献
994.
We study a rechargeable lithium-ion battery that uses a many-particle FePO4 electrode to reversibly store lithium atoms. This process is accompanied by a phase transition and charging/discharging run along different paths, so that hysteretic behavior is observed.Although there are experimental studies suggesting that the overall behavior of the battery is a many-particle effect, most authors exclusively describe the phase transition within a single particle model of the electrode.In this work, we study in detail a many-particle model for the electrode. The model is capable to describe a kind of phase transition where each individual particle of the electrode is homogeneous. It will be shown that the particles are either in the first phase or in the second phase. This phenomenon is due to the non-monotone relation between the chemical potential and the lithium mole fraction of a single particle.The pressure-radius relation of a spherical elastic rubber balloon also exhibits non-monotone behavior. In fact, a system of many interconnected balloons behaves correspondingly to an electrode consisting of many storage particles. The analogy between the two systems is important, because the predictions of the many-particle model can easily be tested with rubber balloons of macroscopic size than with an ensemble of microscopically small (FePO4) particles. 相似文献
995.
Christian Niedrig Simon TaufallMónica Burriel Wolfgang MenesklouStefan F. Wagner Stefan Baumann 《Solid State Ionics》2011,197(1):25-31
Ba0.5Sr0.5Co0.8Fe0.2O3 - δ (BSCF) is a material with excellent oxygen ionic and electronic transport properties reported by many research groups. In its cubic phase, this mixed ionic-electronic conducting (MIEC) perovskite is a promising candidate for oxygen permeation membranes. For this application, its long-term stability under operating conditions (especially temperature and oxygen partial pressure) is of crucial importance.The present work is focused on the thermal stability of the BSCF cubic phase in the targeted temperature range for applications (700…900 °C) in light of previous studies in literature reporting a reversible transition to a hexagonal phase somewhere below 900 °C.To this end, single phase cubic BSCF powders were annealed at different temperatures over varying periods of time. Phase composition was subsequently analysed by X-ray diffractometry (XRD) in order to determine both the temperature limit and the time-scale for the formation of the hexagonal phase. Additionally, the long-term behaviour of the electrical conductivity was examined on bulk samples at 700 °C, 800 °C and 900 °C over several hundreds of hours, showing a prolonged decrease at 800 °C. The decrease in electrical conductivity at this temperature was also examined on bulk samples with different grain sizes, showing a more pronounced decrease the smaller the average grain size.Coexistence of both phases (cubic and hexagonal) could also be shown for 700 °C, however with a different phase equilibrium than at 800 °C. 相似文献
996.
997.
In the context of finite-element simulations of porous media, computing time and numerical effort is an important issue because the number of degrees of freedom of such coupled problems can become very large. Following this, model reduction plays an important role. A broad variety of materials exhibit a porous microstructure. In order to evaluate the overall response of these materials, a macroscopic continuum-mechanical modelling approach is used. Therefore, the complex inner structure of porous media is regarded in a multi-phasic and multi-component manner by means of the well-founded Theory of Porous Media (TPM). The mechanical behaviour of porous media is solved using the Finite-Element Method (FEM). The basic idea of model reduction is to transform a high dimensional system, in terms of the system's degrees of freedom, to a low dimensional subspace to minimise the computational effort while maintaining the accuracy of the solution. The method of proper orthogonal decomposition (POD) can be seen as a method to approximate a given data set with a low dimensional subspace. Furthermore, the POD method is independent of the type of the model and can be used for nonlinear systems as well as for systems of second order. In several applications, such as consolidation problems of partially saturated soils, commonly occurring motion sequences can be found, which can be used as typical “snapshots” of the system. Therefore, the application of the POD method to the simulation of porous media is discussed in the present contribution. Investigated computations of a biphasic standard problem show that the POD method reduces the numerical effort to solve the linearised system of equations in each iteration step. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
998.
999.
Christian Hammer Benjamin Walther Hikmet Karabulut Manuel M. Lohrengel 《Journal of Solid State Electrochemistry》2011,15(9):1885-1891
Anodic Ta oxide films are said to inhibit oxygen evolution. In industry, however, large amounts of gas are evolved during
the anodization of tantalum anodes for electrolytic capacitor fabrication. We quantified the oxygen by fluorescence quenching
in a flow-through cuvette and found that 4% of the anodic charge are consumed for oxygen evolution. In wires or sheets, this
oxygen is removed by diffusion without bubble formation and, thus, not recognized. Due to the large inner area of the sintered
Ta anodes, the oxygen evolution causes strong oscillations of the current density and bubble formation. The amount of oxygen
is proportional to the oxide amount formed in parallel. This is explained by a model where mobile ions during oxide growth
form interband states which allow electron tunneling. Accordingly, stationary no oxygen evolution is observed. 相似文献
1000.
Dr. Matthias C. Witschel Dr. H. Wolfgang Höffken Michael Seet Dr. Liliana Parra Thomas Mietzner Frank Thater Dr. Ricarda Niggeweg Dr. Franz Röhl Dr. Boris Illarionov Dr. Felix Rohdich Dr. Johannes Kaiser Prof. Dr. Markus Fischer Prof. Dr. Adelbert Bacher Prof. Dr. François Diederich 《Angewandte Chemie (International ed. in English)》2011,50(34):7931-7935