Continuum Model for Electronic Polarization Based on a Novel Dielectric Response Function

基于连续介质模型推导了一个普适的描述电介质介电弛豫过程的响应函数. 该介电响应函数依赖于电介质的介电谱. 基于该函数推导得到了以前特殊情况下用于描述溶剂弛豫的响应函数一致的表达式.结合三种典型极性溶剂,水、甲醇和乙腈的介电谱,研究了三种溶剂在外加电场线性变化时的电子极化过程. 结果表明,溶剂的电子极化伴随着电子跃迁同步发生,没有时滞.     

结合有效介质理论的乳状液太赫兹光谱分析

原油乳状液对原油的长距离输运具有重要影响,乳状液的油、水状态及相互作用机制还需新理论和新方法获得新认识,基于有效介质理论,本文研究了原油乳状液太赫兹光谱响应特征.通过太赫兹时域光谱系统测试得到了含水率为0～28％的原油乳状液的太赫兹时域光谱,结合傅里叶变换计算了吸收系数和介电常数等光学参数,同一频率下吸收系数等光学参数...     

Dipolar correlations and the dielectric permittivity of water

The static dielectric properties of liquid and solid water are investigated within linear response theory in the context of ab initio molecular dynamics. Using maximally localized Wannier functions to treat the macroscopic polarization we formulate a first-principles, parameter-free, generalization of Kirkwood's phenomenological theory. Our calculated static permittivity is in good agreement with experiment. Two effects of the hydrogen bonds, i.e., a significant increase of the average local moment and a local alignment of the molecular dipoles, contribute in almost equal measure to the unusually large dielectric constant of water.     

Triple gauge couplings in polarised e^-e^+ \rightarrow W^-W^+ and their measurement using optimal observables

The sensitivity of optimal integrated observables to electroweak triple gauge couplings is investigated for the process fermions at future linear colliders. By a suitable reparameterisation of the couplings we achieve that all 28 coupling parameters have uncorrelated statistical errors and are naturally normalised for this process. Discrete symmetry properties simplify the analysis and allow checks on the stability of numerical results. We investigate the sensitivity to the couplings of the normalised event distribution and the additional constraints that can be obtained from the total rate. Particular emphasis is put on the gain in sensitivity one can achieve with longitudinal beam polarisation. We also point out questions that may best be settled with transversely polarised beams. In particular we find that with purely longitudinal polarisation one linear combination of coupling parameters is hardly measurable by means of the normalised event distribution. Received: 25 September 2002 / Published online: 19 February 2003     

Theory and simulation of chain molecules with multiple bonding sites in an associating solvent

Although polyethylene oxide (PEO) is soluble in water, polymethylene oxide (PMO) is not, even though PMO has more association sites. Some suggest this is due to orientation effects in the water hydrogen-bond network. A simulation and theory study of the effect of bonding site density on thermodynamic properties and extent of bonding of a linear flexible chain in a hydrogen-bonding solvent is performed. Predictions from Wertheim's theory are compared against simulation results. Thermodynamic properties and extent of bonding were obtained. The solvent molecules are modeled as hard spheres with four association sites in a tetrahedral arrangement. The chains are flexible and consist of six tangent segments of hard spheres with bonding sites that interact with the solvent molecules. A solvent molecule can also form a bond with a second solvent molecule. The association interaction is modeled with an orientation-dependent square-well. The total number of bonding sites on each chain is varied and the effects studied. This is another test of the theory for the case of mixtures of associating molecules of different sizes. The Metropolis Monte Carlo technique was chosen to perform simulations in the canonical and isothermal–isobaric ensembles. Good agreement was found between theory and simulation.     

On the theory of dielectric spectroscopy of protein solutions

We present a theory of the dielectric response of solutions containing large solutes, of the nanometer size, in a molecular solvent. It combines the molecular dipole moment of the solute with the polarization of a large subensemble of solvent molecules at the solute-solvent interface. The goal of the theory is two-fold: (i)?to formulate the problem of the dielectric response avoiding the reliance on the cavity-field susceptibility of dielectric theories and (ii)?to separate the non-additive polarization of the interface, jointly produced by the external field of the laboratory experiment and the solute, from specific solute-solvent interactions contributing to the dielectric signal. The theory is applied to experimentally reported frequency-dependent dielectric spectra of lysozyme in solution. The analysis of the data in the broad range of frequencies up to 700?GHz shows that the cavity-field susceptibility, critical for the theory formulation, is consistent with the prediction of Maxwell's electrostatics in the frequency range of 10-200?GHz, but deviates from it outside this range. In particular, it becomes much smaller than the Maxwell result, and shifts to negative values, at small frequencies. The latter observation implies a dia-electric response, or negative dielectrophoresis, of hydrated lysozyme. It also implies that the effective protein dipole recorded by dielectric spectroscopy is much smaller than the value calculated from the protein's charge distribution. We suggest an empirical equation that describes both the increment of the static dielectric constant and the decrement of the Debye water peak with increasing protein concentration. It gives fair agreement with broad-band dispersion and loss spectra of protein solutions, but misses the δ-dispersion region.     

An association theory for the formation of ion oligomers and its application to 1-1 electrolytes

A theory for modelling electrolyte solutions which includes the formation of ion clusters of different size has been developed in the framework of the primitive model. In primitive models the solvent is described as a dielectric continuum and the solvent–solute interactions are neglected. For the dielectric constant the value of the pure solvent has been used. The ion cluster distribution is calculated from the mass action law. The association constants are related to integrals over the cluster distribution functions which are calculated with the Kirkwood superposition approximation from low density pair distribution functions. The ion clusters are defined by a certain distance which rules if two ions belong to the same cluster. This so-called Bjerrum distance is chosen according to fundamental investigations of the structure of ion cluster. All ion clusters are modelled as hard spheres. For the free ions and charged clusters the mean spherical approximation expression for the Coulomb interaction is added. The co-volumes of the ion clusters have been taken from the investigation of the ion cluster structures, and are consistent with the definition of an ion cluster chosen here.     

溶剂对镍连二硫烯与乙烯反应的影响

用密度泛函理论在B3LYP/6-31G(d)水平上计算得到了镍连二硫烯与乙烯反应的势能面上各驻点(反应物、中间体、产物和两个过渡态)的分子几何构型、电荷分布和一些热力学参数等,研究了溶剂对镍连二硫烯与乙烯反应的影响.结果发现,随着溶剂极性的增强,乙烯和镍连二硫烯之间的成键作用增强,两个过渡态的前线轨道能量差增大,而产物和中间体的前线轨道能量差却减小,同时各驻点的溶剂稳定化能也减小.进一步,这表明溶剂极性增强能提高产物的稳定性,有利于反应的进行.此外,当溶剂相对介电常数1.00≤ε≤7.58时 关键词： 镍连二硫烯 乙烯 溶剂效应 密度泛函理论     

快速C60离子团在固体中的库仑爆炸过程Ⅱ分子动力学模拟

研究了快速C60 离子团与固体材料的相互作用过程 .借助于线性介电响应理论及等离子 极点近似介电函数 ,推导出作用在团簇中单个离子上的动力学相互作用力 ,并建立了一套描述离子团中单个离子运动的方程组 .通过数值求解运动方程组 ,可以发现 ,对于高速C60 离子团在固体中穿行时 ,由于动力学相互作用力的影响 ,使得库仑爆炸图形呈现出很强的非球对称性 ,即离子团中的导航离子群爆炸得较快 ,而尾随离子群则保持相对地稳定     

溶剂对镍连二硫烯与乙烯反应的影响

用密度泛函理论在B3LYP/6-31G(d)水平上计算得到了镍连二硫烯与乙烯反应的势能面上各驻点(反应物、中间体、产物和两个过渡态)的分子几何构型、电荷分布和一些热力学参数等，研究了溶剂对镍连二硫烯与乙烯反应的影响.结果发现，随着溶剂极性的增强，乙烯和镍连二硫烯之间的成键作用增强，两个过渡态的前线轨道能量差增大，而产物和中间体的前线轨道能量差却减小，同时各驻点的溶剂稳定化能也减小.进一步，这表明溶剂极性增强能提高产物的稳定性，有利于反应的进行.此外，当溶剂相对介电常数1.00≤ε≤7.58时     

On thermodynamics and mobility of ions enclosed within charged nanoporous system

New simulations and integral equation results are presented for a model partly quenched system composed of monovalent ions. Static and dynamic properties of the system are explored using the replica Ornstein–Zernike theory in the hypernetted chain approximation and Brownian dynamic simulations. The model system consists of two subsystems: one is a collection of charged obstacles (matrix), and the other is an invading electrolyte. The overall system is electroneutral, while the subsystems are not. Charged species are represented by Lennard–Jones spheres of equal size, with either positive or negative charge in the center. The solvent is treated as a continuous dielectric. The purpose of this study is to correlate the mobility of ions (self-diffusion coefficients) with their individual activity coefficients. In addition, the effects of the matrix preparation and of the conditions of observation (dielectric constant of solvent, temperature) are investigated. For the first time, the effect of the charged obstacles on the excess internal energy of the electrolyte solution is also examined.     

MO LCAO calculation of the effect of the reaction electric field on the constant of the spin-spin interaction for P31 and H1 in phosphine

Perturbation theory is used in the MO LCAO approximation to derive a general relation between the constant of the spin-spin interaction and the reaction electric field. This relation predicts possible changes in this constant when there are changes in the dielectric constant of the solvent. The magnitude and nature of these changes depend on the magnitude and orientation of the dipole moment of the dissolved molecule with respect to the direction of the chemical bonds of the interacting nuclei in this molecule. A quantitative calculation is carried out for the effect of the reaction electric field on the spin-spin constant in the PH₃ molecule. A satisfactory agreement is found with experiment.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii Fizika, No. 10, pp. 38–41, October, 1970.     

Electro-optical properties of dilute solutions of flexible molecules ; the wormlike chain model

A theory of propagation and scattering of light in dilute solutions of flexible chain molecules is developed. The solvent is represented as a continuous isotropic dielectric medium. The polymer molecules are modelled as dielectric objects which may have an anisotropic dielectric tensor. The theory, applied to the wormlike chain model, represents the polymer molecules as flexible cylinders of constant cross section and with an isotropic internal dielectric constant. The increment in the refractive index of the solution and the isotropic and anisotropic light scattering intensities due to the presence of the chain molecules are derived. The numerical results of our model for the depolarization ratio as a function of the contour length and the persistence length of the polymer and of the refractive index of the solvent are presented and compared with the corresponding results for the popular bond additive approximation (BAA). It is found that the differences between our model and this approximation are due to the neglect of intramolecular dipole-induced dipole interactions in the BAA.     

快速C60离子团在固体中的库仑爆炸过程Ⅰ球壳层模型

研究了快速C60 离子团在固体中穿行时的库仑爆炸过程 .假定离子团中离子之间位置矢量的取向是随机的 ,并且采用球壳模型描述C60 离子团的结构 .借助于线性介电响应理论和等离子 极点近似介电函数 ,推导出C60 离子团自能的解析表达式 .通过数值求解描述离子团半径变化的运动方程 ,可以发现自能中的“尾效应”可以降低C60 离子团的库仑爆炸速度 ,甚至可以稳定C60 离子团的结构     

Finite size effect of ions and dipoles close to charged interfaces

The modified dipolar Poisson-Boltzmann(MDPB) equation,where the electrostatics of the dipolar interactions of solvent molecules and also the finite size effects of ions and dipolar solvent molecules are explicitly taken into account on a mean-field level,is studied numerically for a two-plate system with oppositely charged surfaces.The MDPB equation is solved numerically,using the nonlinear Multigrid method,for one-dimensional finite volume meshes.For a high enough surface charge density,numerical results of the MDPB equation reveal that the effective dielectric constant decreases with the increase of the surface charge density.Furthermore,increasing the salt concentration leads to the decrease of the effective dielectric constant close to the charged surfaces.This decrease of the effective dielectric constant with the surface charge density is opposite to the trend from the dipolar Poisson-Boltzmann(DPB) equation.This seemingly inconsistent result is due to the fact that the mean-field approach breaks down in such highly charged systems where the counterions and dipoles are strongly attracted to the charged surfaces and form a quasi two-dimensional layer.In the weak-coupling regime with the electrostatic coupling parameter(the ratio of Bjerrum length to Gouy-Chapman length) Ξ 1,where the MDPB equation works,the effective dielectric constant is independent of the distance from the charged surfaces and there is no accumulation of dipoles near the charged surfaces.Therefore,there are no physical and computational advantages for the MDPB equation over the modified Poisson-Boltzmann(MPB) equation where the effect of dipolar interactions of solvent dipoles is implicitly taken into account in the renormalised dielectric constant.     

Multipole analysis of a generic system of dielectric cylinders and application to fibrous materials

A multipole theory describing the interactions between dielectric cylinders in a uniform field is developed. We treat the most general case of $N$ parallel cylinders placed in arbitrary positions. The exact theory is obtained by developing the polarisation charge surface density on each cylinder in a Fourier series. The related coefficients, the so-called multipoles, may be obtained from a linear set of equations which is derived and analysed in the paper. For systems of closely spaced cylinders, with high ratio of the dielectric constant of the cylinders compared to that of the homogeneous medium (in the worst case, conductive cylinders in contact with each other) a very large number of multipole terms is required to achieve convergence. In spite of the large number of required terms, the general multipole expansion is rapidly convergent in all other cases and is important from a theoretical point of view. Numerical results are presented for canonical dispositions of cylinders and for more complicated arrangements. Finally, such a multipole expansion has been applied to the dielectric characterisation of composite materials formed by a regular array of parallel cylinders, thereby obtaining the equivalent permittivity using a numerically efficient technique.     

Frequency dependence of microwave-assisted electron-transfer chemical reactions

In this paper, the electron transfer reactions in the microwave field are studied. A classical theory is developed for a mix of reagents and polar frequency-dispersive and lossy solvent filling vessels excited by microwaves. These reactors are described by a system of non-linear partial self-consistent differential equations for non-stationary microwave field, heat and liquid dynamics, and chemical molecular kinetics. A particular solution of this system is considered for the isothermic electron-transfer reactions in the microwave field varying its frequency with the calculation of the normalised Marcus rate coefficient. It is found that for the small normalised reaction free energy, the chemical reactions are supported by microwaves in a wide frequency band with an increased value of the exponent in the Marcus rate coefficient. At higher values of this energy, these reactions are driven only by conventional microwave heating. The restrictions for the given theory are reviewed, and further experimental and semi-classical and quantum-mechanical studies are found essential for practical applications of these findings.     

CuS纳米粒子在太赫兹波段的光电性质研究

关键词： 太赫兹 CuS纳米粒子 Lorentz理论 Drude-Smith模型     

Ab-initio calculation of optical properties of AA-stacked bilayer graphene with tunable layer separation

Density functional theory based calculations revealed that optical properties of AA-stacked bilayer graphene are anisotropic and highly sensitive to the interlayer separation. In the long wave length limit of electromagnetic radiation, the frequency dependent response of complex dielectric function becomes vanishingly small beyond the optical frequency of 25.0 eV. Besides, static dielectric constant shows a saturation behaviour for parallel polarization of electric field vector when interlayer spacing is greater than 2.75 Å. As a consequence, an appropriate modification of effective fine structure constant is observed as a function of layer separation. Moreover, the bilayer systems are highly transparent in the optical frequency range of 7.0–10.0 eV. The electron energy loss function exhibits two different in-plane collective (plasmon) excitations and a single out of plane plasmon excitation. The spectral nature of different frequency dependent optical properties is observed to be very similar to that of the monolayer pristine graphene apart from their exact numerical values.