Mechanisms responsible for chemical shifts of core-level binding energies and their relationship to chemical bonding

A comprehensive review of different mechanisms which contribute to the chemical shifts of core-level binding energies, BEs, is made. A principle focus is on showing how the mechanisms can be used to relate the BE shifts to features of the chemical bonding and chemical interactions in the studied system. Several initial state mechanisms are identified; while some are well known, the importance of others has been only recognized fairly recently. A theoretical framework is presented which places the analysis and interpretation of these BE shifts on a firm foundation. A rigorous definition and distinction of initial and final state effects is presented. This definition is applied to show that initial state effects are often the dominant factors for the chemical BE shifts. It is also shown that, in many cases, theoretical approaches involving the use of constrained variations can permit a clear and definitive separation of the contributions of the different mechanisms. Several representative applications to the analysis and interpretation of core-level BE shifts are described which show how the theoretical methods of analysis can be used to identify the mechanisms important for the BE shifts. Often more than one mechanism makes an important contribution to the shifts and it is common that the contributions will be canceling. When all of the relevant mechanisms are taken into account in the analysis of the BE shifts, these shifts do provide valuable information about the chemical bonding and electronic structure of the materials being studied. The mechanisms presented and the theoretical frameworks described provide a unified view of BE chemical shifts.     

PSM studies III. A model of post-stimulatory masking phenomena

The experimental results obtained from a study of post-stimulatory masking phenomena are summarized. Two mechanisms are postulated to explain these results. A model, based on these two mechanisms, is derived, and comprises the input from the auditory senses, on which preliminary decisions and actions are taken, followed by a selective filter and limited capacity channel leading to the higher brain centres which can effect overriding control on the system. This model is used to provide explanations of the experimental results obtained in this study.     

Spectral integral representations of volume scattering in sediments in layered waveguides

In situ measurements of scattering strength are often obtained by analyzing the early-time, high-angle reverberation from bottom and subbottom features. In order to provide insight into the mechanisms which cause bottom reverberation, and to their distinguishing characteristics, it is necessary to have a capability for modeling both the rough surface and the volume scattering mechanisms. For high-angle, early-time backscatter, the most appropriate approach is to use a spectral integral representation, which naturally includes the continuous spectrum important for this angular regime. A rough surface scattering theory developed earlier in this framework has provided important insights into wave scattering and penetration physics at the seafloor. Here a consistent representation for the subbottom scattering is developed and examples are provided which illustrate the observable differences between the two scattering mechanisms.     

Air-related mechanisms of noise generation by solid rubber tyres with cavities

There are four main air-related noise generation mechanisms at the tyre/road interface, which were all categorised more than 20 years ago. The first one is the so-called ‘air pumping’ mechanism. Two other air-related phenomena that occur when there are air movements near the contact patch of the tyre are ‘air resonant radiation’ and ‘pipe resonances’ which appear at the footprint of the tyre. In addition to these, there is a forth effect, which is mentioned in the literature, that is occurring due to turbulence effects of the air surrounding the spinning tyre. There has been less focus on the air-related mechanisms than on other types of tyre noise generation mechanisms. This paper attempts to add some detail to current understanding of the air-related noise generation at the tyre road interface and gives some further information on how to identify the differences due to these mechanisms. Specifically in the present paper, a solid rubber tyre running on a vehicle chassis dynamometer is used to study the first two mechanisms. This is done with emphasis on the time history of the recorded signal and not on the frequency spectrum, as is more commonly used. A comparison with existing theoretical models of these mechanisms reveals some of the strength and weaknesses of the current understanding of these phenomena.     

The thermoluminescence mechanism for amino acids

A simple physical model is proposed to explain intensity as a function of temperature, which is based on random excitation and emission. The possible mechanisms are discussed.     

等离子体中的颗粒成长模型

研究等离子体环境下的带电微小颗粒的成长过程．在收集离子和颗粒间凝合两种成长机制中,后者起主要作用,使生成的颗粒粒度接近．基于能量均分定理提出一个简化的模型,推导出颗粒粒度分布函数的动力方程．初步的数值模拟结果证实了上述成长机制的设想. 关键词：     

Combination Mechanisms of Ionization and Recombination and Generation-Recombination Processes in Semiconductors

A new combination mechanism of recombination – collision-thermal (CT) one – is suggested in the present paper. The corresponding recombination coefficients are calculated for pure and doped Ge samples. Conditions at which the CT recombination mechanism becomes dominant over the Lax cascade mechanism are elucidated. A numerical experiment, which takes into account the combination mechanisms of ionization and recombination and the process of electron transfer by impurity centers, is performed.     

The dual twin image effect from a waveguide hologram

A new phenomenon called the dual twin image effect is reported. The mechanisms of the dual twin image effect and the twin image effect are discussed. A sandwich-like waveguide hologram unit, which can be used for fingerprint recognition, is described and verified experimentally.     

The production of primary radicals in photopolymers during holographic exposure

Recently, extensive studies have been carried out on the time varying absorption effects, which occur in photopolymer materials, during holographic exposure. The theoretical analysis presented in these studies, assumed that three primary mechanisms determined the dye kinetic behaviour. These mechanisms are: (i) photon absorption, (ii) the regeneration or recovery of absorptive photosensitiser, and (iii) photosensitiser bleaching. Based on this analysis, the generation of primary radicals were then described. In this article, we significantly extend these theoretical analyses. A detailed examination of the photochemical reactions, which take place during the photo-initiation mechanisms, is presented. Then a more accurate representation of the initiation mechanisms is developed. This enables more exact expressions for both the temporal and spatial variations of the photosensitiser and primary radical concentrations, to be generated.     

Theory of fusion for superheavy elements

A new model is proposed for fusion mechanisms of massive nuclear systems, where so-called fusion hindrance exists. The model describes the whole process in two steps: two-body collision processes in an approaching phase and shape evolutions of an amalgamated system into the compound nucleus formation. It is applied to ⁴⁸Ca-induced reactions and is found to reproduce the experimental fusion cross sections extremely well, without any free parameter. A schematic case is solved in an analytic way, the results of which shed light on fusion mechanisms. Combined with statistical decay theory, residue cross sections for superheavy elements can be readily calculated. Examples are given.     

On the mechanism of liquid metal electron and ion sources

The mechanisms of electron and ion generation from Taylor cones of liquid metals are discussed. In the case of electron emission the vacuum arcing mechanism of Swanson and Schwind, which accounts for the observed high current repetitive pulsing is briefly reviewed. For ion emission mechanisms from onset to the high current regime are proposed. It is concluded that at onset ions are generated exclusively by field desorption. A theory to account for the observed emitter heating is advanced, and it is concluded that high currents result from field ionization of thermally evaporated atoms. It is shown that space charge becomes important even at very low ion currents and'is instrumental in providing stabilization in all regimes of ion emission.     

A new combination of scattering mechanisms for transverse runaway (TR) of hot electrons

A new combination of energy and momentum scattering mechanisms has been found at which the transverse runaway (TR) of hot electrons takes place. Up to now only two combinations of scattering mechanisms at which TR occurred have been known. These two combinations were obtained by analytical solution of a complex integral equation at certain approximations. In the present work, using modern numerical methods, with no above-mentioned approximations, a solution of the integral equation for a new combination of scattering mechanisms has been found.In the work physical conditions responsible for dominance of corresponding scattering mechanisms are also analyzed.     

沙子里的图案

文章从物理学家的角度探讨颗粒体系中有序图案的产生和机理,探寻对广泛存在于自然界的非平衡态体系有序结构生成的理解.非平衡态体系的随机扩散与能量耗散的特性是有序结构生成的必备条件,所生成的图形则由这两个因素的权重比值和体系内部的对称性决定.具备以上因素,还需加上最后的一个决定性的关键因素,这就是熵的驱动.熵最大的态决定了体系是有序还是无序的排列.     

Electron scattering at the grain boundaries and at the external surfaces in polycrystalline metal films

A grain boundary model is proposed for the calculation of metal film conductivity, in which three electron scattering mechanisms operate simultaneously. These are: isotropic background scattering, scattering caused by distributions of potential barriers which represent the grain boundaries, and the electron scattering at the external film surfaces. The electrical conductivity of such films has been calculated.     

Ion-enhanced gas-surface chemistry: The influence of the mass of the incident ion

There are many examples of situations in which a gas-surface reaction rate is increased when the surface is simultaneously subjected to energetic particle bombardment. There are several possible mechanisms which could be involved in this radiation-enhanced gas-surface chemistry. In this study, the reaction rate of silicon, as determined from the etch yield, is measured during irradiation of the Si surface with 1 keV He⁺, Ne⁺, and Ar⁺ ions while the surface is simultaneously subjected to fluxes of XeF₂ or Cl₂ molecules. Etch yields as high as 25 Si atoms/ion are observed for XeF₂ and Ar⁺ on Si. A discussion is presented of the extent to which these results clarify the mechanisms responsible for ion-enhanced gas-surface chemistry.     

Issues arising in the construction of QSSA mechanisms: the case of reduced n-heptane/air models for premixed flames

A model reduction methodology, based on the quasi steady-state approximation (QSSA), is employed for the construction of reduced mechanisms in the case of an n-heptane/air premixed flame. Several issues related to the construction of these reduced mechanisms are discussed; such as the influence of the size of the starting skeletal mechanism, the stiffness reduction, and the truncation/simplification of (i) the expressions of the global rates and (ii) the steady-state relations. The starting point for the reduction is two skeletal mechanisms that involve 177/768 and 66/326 species/reactions, respectively [J. Prager, H.N. Najm, M. Valorani, and D.A. Goussis, Skeletal mechanism generation with CSP and validation for premixed n-heptane flames, Proc. Combust. Inst. 32 (2009), pp. 509–517] and which were derived from the detailed mechanism of Curran et al. [H.J. Curran, P. Gaffuri, W.J. Pitz, and C.K. Westbrook, A comprehensive modeling study of iso-octane oxidation, Combust. Flame 129 (2002), pp. 253–280], which involves 561/2538 species/reactions. From these two skeletal mechanisms, a number of reduced mechanisms of various sizes are produced and analysed. The validity of the reduced mechanism with the minimum size is demonstrated by considering its accuracy regarding the mass fractions of major and minor species, the temperature, and the flame speed, over a wide range of equivalence ratios and pressures.     

Cross-field transport by instabilities and blobs in a magnetized toroidal plasma

The mechanisms for anomalous transport across the magnetic field are investigated in a toroidal magnetized plasma. The role of plasma instabilities and macroscopic density structures (blobs) is discussed. Examples from a scenario with open magnetic field lines are shown. A transition from a main plasma region into a loss region is reproduced. In the main plasma, which includes particle and heat source locations, the transport is dominated by the fluctuation-induced particle and heat flux associated with a plasma instability. On the low-field side, the cross-field transport is ascribed to the intermittent ejection of macroscopic blobs propagating toward the outer wall. It is shown that instabilities and blobs represent fundamentally different mechanisms for cross-field transport.     

Using temperature to tune film roughness: nonintuitive behavior in a simple system

Ag(100) homoepitaxy constitutes one of the simplest systems in which to study thin-film growth. Yet we find that the roughness variation with temperature is extraordinarily complex. Specifically, as the deposition temperature is reduced from 300 to 50 K, the roughness of 25 monolayer films first increases, then decreases, then increases again. A transition from mound formation to self-affine (semifractal) growth occurs at approximately 135 K. The underlying mechanisms are postulated. An atomistic model incorporating these mechanisms reproduces the experimental data quantitatively.