电场作用下S修饰C24N24从CO2/N2混合气体中选择性吸附

在燃烧后气体中选择性捕获CO2,对减缓因CO2浓度过高引发的环境问题具有十分重要的意义。本文采用第一性原理计算的方法,研究了外加电场作用下S修饰C24N24富勒烯对CO2的选择性吸附性能。首先研究了S@C24N24的结构和性质,发现其具有良好的稳定性。其次,研究了无电场时S修饰C24N24富勒烯对CO2的吸附行为,发现其吸附为弱的物理吸附。另外,进一步研究了外加电场作用下S@C24N24对CO2的吸附行为。结果表明,结合距离（CO2与S）和CO2的键角（O=C=O）随电场的增大而减小;当电场增加到0.018 au时,物理吸附转变为化学吸附。关闭电场时,化学吸附又转化为物理吸附。此外,即使在相同的电场条件下,S修饰C24N24富勒烯对N2的吸附也为弱的物理吸附。这表明,通过控制外加电场的开/关,S@C24N24可以从CO2/N2混合气体中选择性捕获/释放CO2,可作为选择性捕获CO2的优良候选材料。     

外电场对CO分子及离子性质的调制和降解

基于密度泛函理论(DFT)的B3LYP方法,在6-311G++基组水平上,计算研究外加电场下CO分子及离子物理性质,包括总能量、键长、电荷分布、能级分布和红外光谱,并根据势能曲线研究CO外加电场下的降解。随着外电场逐渐增大(- 0.015 a. u.~0.015 a. u.),CO的性质发生明显的变化, 电场增大到一定程度时可实现CO分子降解。同样,CO⁺离子的总能量随电场的增大逐渐减小,键长变长,偶极矩逐渐变大,分子能隙在Alpha轨道中逐渐减小,在Beta轨道中逐渐增大,红外光谱的强度相应逐渐增大。电场从0.0 a. u增大到0.150 a. u.时,势能曲线的变化同样表明CO⁺离子离解能减小。电场增大到一定程度时可实现CO⁺离子降解。     

金属纳米椭球结构表面的局域电场和吸附分子分布

过渡金属纳米结构表面吸附CO分子时会出现异常红外效应,这一现象可以用纳米结构表面吸附分子在外电场作用下产生局部凝聚从而相互作用能增加来解释.在前期研究的基础上,给出金属基底表面生长出的纳米颗粒为椭球状颗粒的理论计算结果.基于均匀外电场中金属纳米椭球颗粒按一定对称性排列的表面结构模型,用经典电磁学理论计算了纳米椭球颗粒表面附近的局域电场.在此基础上,将吸附的CO分子等效为偶极子,在考虑了偶极子与局域电场、偶极子之间以及偶极子与金属基底三种相互作用的情况下,用Monte-Carlo方法进行数值模拟,最后给出纳 关键词： 金属纳米结构表面 纳米椭球 吸附分子 局域电场     

Local electric field and configuration of CO molecules adsorbed on a nanostructured surface with nanocones

Based on the nanostructured surface model that the (platinum, Pt) nanocones grow out symmetrically from a plane substrate, the local electric field near the conical nanoparticle surface is computed and discussed. On the basis of these results, the adsorbed CO molecules are modelled as dipoles, and three kinds of interactions, i.e. interactions between dipoles and local electric field, between dipoles and dipoles, as well as between dipoles and nanostructured substrate, are taken into account. The spatial configuration of CO molecules adsorbed on the nanocone surface is then given by Monte-Carlo simulation. Our results show that the CO molecules adsorbed on the nanocone surface cause local agglomeration under the action of an external electric field, and this agglomeration becomes more compact with decreasing conical angle, which results in a stronger interaction among molecules. These results serve as a basis for explaining abnormal phenomena such as the abnormal infrared effect (AIRE), which was found when CO molecules were adsorbed on the nanostructured transition-metal surface.     

Role of the Radiation‐Reaction Electric Field in the Optical Response of Two‐Dimensional Crystals

A classical theory of a radiating two‐dimensional crystal is proposed and an expression for the radiation‐reaction electric field is derived. This field plays an essential role in connecting the microscopic electromagnetic fields acting on each dipole of the crystal to the macroscopic one, via the boundary conditions for the system. The expression of the radiative‐reaction electric field coincides with the macroscopic electric field radiating from the crystal and, summed to the incident electric field, generates the total macroscopic electric field.     

Burning carbon monoxide in the settling chamber of a hotshot wind tunnel for obtaining the CO<Subscript>2</Subscript> test gas

A method of formation and heating of CO₂ as a test gas in the settling chamber of a hotshot wind tunnel is considered. To form and heat CO₂, the chamber is filled with a source gas mixture of CO, O₂, and CO₂, and after initiation, these substances participate in an exothermic chemical reaction in accordance with the formula CO + 0.5 O₂ + xCO₂ = (1 + x)CO₂. A stoichiometric ratio of the concentrations of carbon monoxide CO and oxygen is used. Variation of the number of moles x of ballast CO₂ in the left part of the chemical formula allows changing the temperature of the resultant test gas in a wide range. Experiments in the IT-302M hotshot wind tunnel carried out at ITAM SB RAS have shown that a pressure increase during an isochoric process in the settling chamber due to the joint effect of heat released in the reaction CO + 0.5 O₂ and an electric charge provides the completeness of CO combustion almost equal to unity. The time of reaction completion at its initiation by an electric arc is no more than several milliseconds.     

Local field distribution and configuration of CO molecules adsorbed on the nanostructure platinum surface

This paper shows that the local electric field distribution near the nanostructure metallic surface is obtained by solving the Laplace equation, and furthermore, the configuration of CO molecules adsorbed on a Pt nanoparticle surface is obtained by using Monte Carlo simulation. It is found that the uneven local electric field distribution induced by the nanostructure surface can influence the configuration of carbon monoxide (CO) molecules by a force, which drags the adsorbates to the poles of the nanoparticles. This result, together with our results obtained before, may explain the experimental results that the nanostructure metallic surface can lead to abnormal phenomena such as anti-absorption infrared effects.     

Influence of the electric field on the electron transport in photosynthetic reaction centers

The effect of an electric field on the electron transfer in the bacterial reaction centers is investigated. The rate constants and quantum yields affected by the electric field for wild type (WT) and reaction center (RC) mutant of Rhodobacter capsulatus were computed. The dependence of the asymmetry of electron transfer in electric field on the temperature was evaluated. We found stable electron transfer for WT of the reaction center towards an electric field in comparison with the F(L121)D mutant of RC. We found quantum yields sensitive to the variation of the medium reorganization energy at low temperatures and strong electric fields. The quantum yields for unoriented RC samples were also calculated.     

金属纳米结构表面吸附的CO分子在外电场中的相互作用

建立金属纳米颗粒在外电场中的排列结构模型，用经典理论分析纳米结构金属表面上吸附的CO分子在外电场中的相互作用能，包括有效偶极子间的相互作用和与局域电场的相互作用，并讨论和计算了纳米颗粒表面附近的局域电场. 用Monte-Carlo方法进行数值计算和模拟，具体给出纳米颗粒表面CO分子的分布和相互作用能，表明金属表面纳米结构使CO产生凝聚，并使分子相互作用能增加，为解释异常红外吸收效应提供依据. 关键词： 纳米结构金属 吸附分子 相互作用 局域电场     

金属纳米锥表面吸附分子分布的数值模拟

在均匀外电场中,将吸附在由过渡金属基底生长的纳米锥颗粒表面的CO分子等效为偶极子,在考虑偶极子与局域电场,偶极子之间色散力及偶极子与锥表面原子之间三种相互作用的情况下,给出各相互作用能的数学模型,并用Monte Carlo方法进行数值模拟,得到纳米锥颗粒表面吸附CO分子的空间分布构型.结果表明,在这些相互作用下,纳米锥表面吸附CO分子产生局部凝聚,且随着纳米锥角的变小,吸附在锥顶部的分子更加密集,导致吸附分子间相互作用更强,为解释纳米结构表面吸附体系的异常红外效应提供依据.     

Quasi-pyroelectricity in the TGS crystal

It has been shown that a side electrode perpendicular to the measurement ones can significantly enhance the transverse electric current in TGS. Such a current, measured in a zero external electric field, resembles the classic longitudinal one. However, the amplitude of the transverse current oscillation, observed while cooling and heating the sample, rises much more slowly with the time of the transverse electric field preliminary application. Such exposure to the transverse field is required prior to the measurements for the transverse current to be observed, in a similar way to a longitudinal field that is applied in order to achieve a single domain state before longitudinal pyroelectric current measurements. A huge difference in the time of reaction to the electric fields preliminarily applied in order to achieve the maximum amplitude of the current oscillations in both cases is the evidence that the transverse current cannot be considered to be originated just for geometrical reasons.     

The topography of nickel crystals during the reaction towards Ni(CO)4; A field ion microscope study

The structural aspect of the formation of Ni(CO)₄ by the reaction of CO with solid nickel has been studied. The nickel initial state was a nearly hemispherical single crystal as prepared by field evaporation of a nickel field emitter tip. Field-free reaction of CO with the clean nickel surface took place at pressures up to 2 mbar, reaction times up to 45 h, and at a temperature of 373 K, which as a result from work by others was found optimum for highest rates of Ni(CO)₄ formation. Neon field ion imaging at 80 K after reaction with CO showed the crystal always in an intermediate state, which had the features: (1) Areas of {;111} were increased; (2) at half angles between a central (111) and peripherical {111} planes there were {110} planes flanked by {210}, and {100} flanked by {511}, respectively; (3) with the exception of the planes mentioned in feature (2), the remaining surface area was more than mono-atomically stepped. From these results and in accordance with the theory of crystal growth (Kossel, Stranski) and the theory of crystal dissolution (Lacmann, Franke, Heimann) a pure octahedron is expected to be the final state of the crystal. This implies that nickel atoms removed by the reaction are most frequently taken from 〈110〉 atom chains of the {111} planes.     

TEA CO2激光器均匀场电极的设计

介绍了与此有关的大面积均匀场放电电极的设计以及实验研究结果。无限大平行平板电极两极间的电场分布是均匀的,而现实的问题则是要求在有限的（电极）尺寸条件下实现电场的均匀性设计,因此设计问题转变为放电电极的剖面形状的理论和工程计算问题。根据TEA CO₂激光器工作的实际情况,有针对性地选择Chang氏理论作为设计依据。设计的放电电极实验结果证明,TEA CO2激光器在500HZ高重频脉冲条件下能够连续工作10分钟,在55mm放电电极宽和平坦部分为40mm剖面的平行平板两个主放电极之间实现了大面积稳定的均匀场辉光放电。     

Kinetic parameters,collision rates,energy exchanges and transport coefficients of non-thermal electrons in premixed flames at sub-breakdown electric field strengths

The effects of an electric field on the collision rates, energy exchanges and transport properties of electrons in premixed flames are investigated via solutions to the Boltzmann kinetic equation. The case of high electric field strength, which results in high-energy, non-thermal electrons, is analysed in detail at sub-breakdown conditions. The rates of inelastic collisions and the energy exchange between electrons and neutrals in the reaction zone of the flame are characterised quantitatively. The analysis includes attachment, ionisation, impact dissociation, and vibrational and electronic excitation processes. Our results suggest that Townsend breakdown occurs for E/N = 140 Td. Vibrational excitation is the dominant process up to breakdown, despite important rates of electronic excitation of CO, CO₂ and N₂ as well as impact dissociation of O₂ being apparent from 50 Td onwards. Ohmic heating in the reaction zone is found to be negligible (less than 2% of peak heat release rate) up to breakdown field strengths for realistic electron densities equal to 10¹⁰ cm^?3. The observed trends are largely independent of equivalence ratio. In the non-thermal regime, electron transport coefficients are insensitive to mixture composition and approximately constant across the flame, but are highly dependent on the electric field strength. In the thermal limit, kinetic parameters and transport coefficients vary substantially across the flame due to the spatially inhomogeneous concentration of water vapour. A practical approach for identifying the plasma regime (thermal versus non-thermal) in studies of electric field effects on flames is proposed.     

TEA CO2激光器预电离结构电极系统的电场研究

 高功率气体激光器的非对称复杂电极系统中,电极参数的变化以及预电离结构的引入将会使所设计的均匀电场发生具体的改变。采用高精度有限元方法,对这类复杂电极系统进行建模并且计算其电场分布,根据分析结果更合理地指导激光器设计。对一种典型的非对称复杂电极系统TEA CO₂激光器,应用该方法并结合了预电离过程,研究了引入预电离器导体和变化电极形状对电极表面的电场强度起伏和放电空间的均匀电场面积产生的影响。结果表明:通过这种预先模拟,合理选择电极构型参数和预电离结构安装位置,可以产生性质较好的均匀电场以及效率较高的激光输出。     

EACVD低温合成金刚石薄膜中非线性电场的数值模拟

采用蒙特卡罗模拟方法,研究了电子辅助热丝化学气相沉积(EACVD)技术低温合成金刚石薄膜过程中反应区的非线性电场分布.结果表明:阳极基片附近反应区电场的空间分布按指数规律变化,在一定的偏压条件下,随着气压的变化阳极附近将出现反向电场,对于金刚石薄膜的低温合成中的正离子分子,该反向电场起重要作用.     

New phase transition in the Pr1-xCaxMnO3 system: evidence for electrical polarization in charge ordered manganites

In this Letter a detailed study of the electric field gradient (EFG) across the Pr(1-x)Ca(x)MnO(3) phase diagram and its temperature dependence is given. Clearly, distinct EFG behavior for samples outside or inside the charge order (CO) region are observed. The EFG temperature dependence evidences a new phase transition occurring over the broad CO region of the phase diagram. This transition is discontinuous and occurs at temperatures between the charge ordering and the Néel temperatures. The prominent features observed in the EFG are associated with polar atomic vibrations which eventually lead to a spontaneous local electric polarization below CO transition.     

Efficiency of electric field catalysis in nucleophilic and electrophilic addition to polyenes

The energetics of nucleophilic addition of pyridine to polyenes of various lengths and the corresponding protonation of these polyenes by methyl ammonium fluoride was computationally determined using ab initio methods. These reactions were also studied in the presence of an electric field (2.5 and 5 MV/cm) oriented along the polyene long axis in the direction which will enhance the reaction. Assuming linearity over a long range, and extrapolating the data for 2.5 MV/cm to 10 nm chain length gave a reduction in the activation energy of the nucleophilic addition of 7 orders of magnitudes implying a ~10⁵ rate enhancement. Conversely, the longer the chain, the smaller is the electric field needed to catalyze the reaction. The transition state locations of the various reactions were determined using the slopes of the Ea versus E₀ plots as well as the Marcus α values. It turns out the efficiency of electric field catalysis is a function of the transition state location. The latter is the transition state (more endothermic reaction) and the more efficient is the electric field catalysis. Copyright © 2014 John Wiley & Sons, Ltd.     

Percolative transport in the vicinity of charge-order ferromagnetic transition in a hole-doped manganite

We report measurements of non-linear charge transport in epitaxial (La_1−x Pr _x )_0.7Ca_0.3MnO₃ thin films fabricated on (100) oriented SrTiO₃ single crystals by pulsed laser deposition. The end members of this series, namely Pr_0.7Ca_0.3MnO₃ and La_0.7Ca_0.3MnO₃ are canonical charge-ordered (CO) and ferromagnetic manganites, respectively. The onset of the CO state in Pr_0.7Ca_0.3MnO₃ is manifested by a pronounced insulating behavior below ∼ 200 K. The CO state remains stable even when a large (∼ 2×10⁵ V/cm) electric field is applied across the thin film samples. However, on substitution of Pr with La, a crossover from the highly resistive CO state to a state of metallic character is observed at relatively low electric fields. The current-voltage characteristics of the samples at low temperatures show hysteretic and history dependent effects. The electric field driven charge transport in the system is modelled on the basis of an inhomogeneous medium consisting of ferromagnetic metallic clusters dispersed in a CO background.     

Microscopic derivation of fluctuation formulas for calculating dielectric constants by simulation

A microscopic derivation using the average Maxwell electric field is given for fluctuation formulas for the dielectric constant of a simulation sample for both periodic and reaction field boundary conditions. The reaction field case is for a spherical cavity reaction field. The derivations put both boundary conditions on an equal footing of microscopic theory and the only nonrigorous part of the derivation is the assumption that the region used to average the electric field is large enough. The fluctuation formula for reaction field boundary conditions is rather different from that used heretofore. The method is applied to a subregion of an isolated spherical system.