Molecular dynamics study on water self-diffusion in aqueous mixtures of methanol,ethylene glycol and glycerol: investigations from the point of view of hydrogen bonding

Molecular dynamics simulations have been performed to investigate the aqueous binary mixtures of alcohols, including methanol, ethylene glycol (EG) and glycerol of molalities ranging from 1 to 5 m at the temperatures of 273, 288 and 298 K, respectively. The primary purpose of this paper is to investigate the mechanism of water self-diffusion in water-alcohol mixtures from the point of view of hydrogen bonding. The effects of temperature and concentration on water self-diffusion coefficient are evaluated quantitatively in this work. Temperature and concentration to some extent affect the hydrogen bonding statistics and dynamics of the binary mixtures. It is shown that the self-diffusion coefficient of water molecules decreases as the concentration increases or the temperature decreases. Moreover, calculations of mean square displacements of water molecules initially with different number n of H-bonds indicate that the water self-diffusion coefficient decreases as n increases. We also studied the aggregation of alcohol molecules by the hydrophobic alkyl groups. The largest cluster size of the alkyl groups clearly increases as the concentration increases, implying the emergence of a closely connected network of water and alcohols. The clusters of water and alcohol that interacted could block the movement of water molecules in binary mixtures. These findings provide insight into the mechanisms of water self-diffusion in aqueous binary mixtures of methanol, EG and glycerol.     

Aggregation kinetics in a model colloidal suspension

We present molecular dynamics simulations of aggregation kinetics in a colloidal suspension modeled as a highly asymmetric binary mixture. Starting from a configuration with largely uncorrelated colloidal particles the system relaxes by coagulation-fragmentation dynamics to a structured state of low-dimensionality clusters with an exponential size distribution. The results show that short-range repulsive interactions alone can give rise to so-called cluster phases. For the present model and probably other, more common colloids, the observed clusters appear to be equilibrium phase fluctuations induced by the entropic intercolloidal attractions.     

Coagulation of charged microparticles in neutral gas and charge-induced gel transitions

Coagulation of charged particles was studied using the mean-field Smoluchowski equation. The coagulation equation was generalized for the case of a conserved system of charged particles. It was shown that runaway cluster growth (gelation) solutions exist if the charge-dipole (induced) interaction of clusters is included. When clusters are in thermal equilibrium with the ambient gas, the charge-dipole interaction dramatically enhances the aggregation process and considerably increases the likelihood of a gelation transition.     

Two-dimensional mesoscopic dusty plasma clusters: Structure and phase transitions

A two-dimensional mesoscopic cluster of “dusty plasma” particles, which can be interpreted as a system of microparticles in an rf gas discharge, is investigated. The ground-state configurations and corresponding eigenfrequencies and eigenvectors are found for clusters of N=22–40 particles in a harmonic confining potential. It is shown that a change in the Debye screening length R of the particle charge in the plasma can cause structural transformations of the ground state of the system, manifested as first-order or second-order phase transitions with respect to the parameter R. The disorder (“melting”) of the clusters is analyzed in detail by Monte Carlo simulation and molecular dynamics. By varying the characteristic range of particle interaction in a cluster, it is possible to modulate its thermodynamic properties and the character of the phase transitions, thereby causing a controlled transition of the system into the fully ordered, orientationally disordered, or fully disordered state. The possibility of dusty plasma clusters coexisting in different states is discussed. Zh. éksp. Teor. Fiz. 116, 1300–1312 (October 1999)     

Relaxation dynamics in small clusters: A modified Monte Carlo approach

Relaxation dynamics in two-dimensional atomic clusters consisting of mono-atomic particles interacting through Lennard-Jones (L-J) potential has been investigated using Monte Carlo simulation. A modification of the conventional Metropolis algorithm is proposed to introduce realistic thermal motion of the particles moving in the interacting L-J potential field. The proposed algorithm leads to a quick equilibration from the nonequilibrium cluster configuration in a certain temperature regime, where the relaxation time (τ), measured in terms of Monte Carlo Steps (MCS) per particle, vary inversely with the square root of system temperature (√T) and pressure (P); τ ∝ (P√T)^?1. From this a realistic correlation between MCS and time has been predicted.     

Aun（n=2—9）团簇的几何结构和电子特性

采用密度泛函DFT中的 B3LYP 方法，选择LANL2DZ基组，对Aun（n＝2—9）小团簇的各种可能结构进行优化，得到了它们的基态平衡结构并计算出其原子化能.研究表明：随着团簇尺寸的增大，单个原子的平均原子化能逐渐增大.同时分析了团簇的能级分布、最高占据轨道与最低空轨道之间形成的能级间隙.计算出了电子亲和能和电离势，计算值与实验值非常接近.最后分析了费米能级、电子亲和能和电离势形成“奇－偶”振荡效应的原因. 关键词： Au团簇 平衡几何结构 能隙 电子性质     

Effects of non‐extensive electrons on the sheath of dusty plasmas with variable dust charge

In this study, a detailed investigation of the problem of sheath is presented using the fluid model in a magnetized three‐component dusty plasma system comprising positive ions, dust grains with variable charge and q‐non‐extensive electrons (i.e., the electrons evolve far away from their Maxwellian thermodynamic equilibrium [q = 1]). The effects of q‐non‐extensivity parameter on the plasma sheath parameters are studied numerically. A significant change is observed in the quantities characterizing the sheath with the presence of the super‐extensive electrons (q < 1) and sub‐extensive electrons (q > 1). In addition, based on the orbital motion limited theory, by taking various forces acting on the dust particle into consideration, the dynamics of the dust located within the sheath, that is, the dust grain charging inside the sheath, is examined under different values of q. It is found that the q‐non‐extensivity has affected significantly the dynamics and the charging process of the dust grains in the sheath.     

Molecular simulation of LiCl aqueous solutions

Non-primitive LiCl aqueous electrolyte solutions were studied at 1.0, 5.0 and 10.0 M concentrations by molecular dynamics simulations. It was observed that the ion hydration structure is progressively lost with increasing concentration. The ions are aggregated in small clusters at C = 1.0 M. However, at this concentration, two large clusters were detected that are an initial step in an aggregation process. At C = 5.0 M, the highly unstable ion clustering seems to correspond to an intermediary state between low concentration states with poor aggregation and states where the ions are highly aggregated, as observed at C = 10.0 M where almost all the ions are clustered in one cluster. This cluster does not present a crystal-like structure. The high solubility of LiCl in aqueous solutions can consequently be explained as a result of the large radii difference between the anion and the cation that results in the instability of the ionic aggregates, which makes the formation of crystal seeds difficult.     

Kinetics and energy states of nanoclusters in the initial stage of homogeneous condensation at high supersaturation degrees

The condensation of metal vapor in an inert gas is studied by the molecular dynamics method. Two condensation regimes are investigated: with maintenance of partial pressure of the metal vapor and with a fixed number of metal atoms in the system. The main focus is the study of the cluster energy distribution over the degrees of freedom and mechanisms of the establishment of thermal equilibrium. It is shown that the internal temperature of a cluster considerably exceeds the buffer gas temperature and the thermal balance is established for a time considerably exceeding the nucleation time. It is found that, when the metal vapor concentration exceeds 0.1 of the argon concentration, the growth of clusters with the highest possible internal energy occurs, the condensation rate being determined only by the rate of heat removal from clusters.     

Cluster growth poised on the edge of break-up: Size distributions with small exponent power-laws

In many naturally occurring growth processes, cluster size distributions of power-law form n(s)∝s^−τ with small exponents 0<τ<1 are observed. We suggest here that such distributions emerge naturally from cluster growth, where size dependent aggregation is counterbalanced by size dependent break-up. The model used in the study is a simple reaction kinetic model including only monomer-cluster processes. It is shown that under such conditions power-law size distributions with small exponents are obtained. Therefore, the results suggest that the ubiquity of small exponent power-law distributions is related to the growth process, where aggregation driven cluster growth is poised on the edge of cluster break-up.     

Synchrotron radiation studies of mass-selected Fe nanoclusters deposited in situ

A portable UHV-compatible gas aggregation cluster source, capable of depositing clean mass-selected nanoclusters in situ, has been used at synchrotron radiation facilities to study the magnetic behaviour of exposed and Co-coated Fe clusters in the size range 250 to 540 atoms. X-ray magnetic circular dichroism (XMCD) studies of isolated and exposed 250-atom clusters show a 10% enhancement in the spin magnetic moment and a 75% enhancement in the orbital magnetic moment relative to bulk Fe. The spin moment monotonically approaches the bulk value with increasing cluster size but the orbital moment does not measurably decay till the cluster size is above ∼ 400 atoms. The total magnetic moments for the supported particles though higher than the bulk value are less than those measured in free clusters. Coating the deposited particles with Co in situ increases the spin moment by a further 10% producing a total moment per atom close to the free cluster value. At low coverages the deposited clusters are super-paramagnetic at temperatures above 10 K but a magnetic remanence at higher temperature emerges as the cluster density increases and for cluster films with a thickness greater than 50 ?(i.e. 2-3 layers of clusters) the remanence becomes greater than that of an Fe film of the same thickness produced by a conventional deposition source. Thick cluster-assembled film show a strong in-plane anisotropy. Received 14 December 2000     

Dynamic percolation transition induced by phase separation: A Monte Carlo analysis

The percolation transition of geometric clusters in the three-dimensional, simple cubic, nearest neighbor Ising lattice gas model is investigated in the temperature and concentration region inside the coexistence curve. We consider quenching experiments, where the system starts from an initially completely random configuration (corresponding to equilibrium at infinite temperature), letting the system evolve at the considered temperature according to the Kawasaki spinexchange dynamics. Analyzing the distributionn _l(t) of clusters of sizel at timet, we find that after a time of the order of about 100 Monte Carlo steps per site a percolation transition occurs at a concentration distinctly lower than the percolation concentration of the initial random state. This dynamic percolation transition is analyzed with finite-size scaling methods. While at zero temperature, where the system settles down at a frozen-in cluster distribution and further phase separation stops, the critical exponents associated with this percolation transition are consistent with the universality class of random percolation, the critical behavior of the transient time-dependent percolation occurring at nonzero temperature possibly belongs to a different, new universality class.     

Dipole moment of a small water cluster. The effect of size,temperature, and electric field

A molecular dynamics simulation of neutral clusters (H₂O) _{n ≤ 21} has been performed in the framework of the flexible polarized model. The formation and evolution of the dipole moment of the cluster have been investigated with a change in the size and temperature of the cluster and an external electric field. It has been shown that at low electric fields corresponding to the experiments on the deflection of clusters in the transverse inhomogeneous electrostatic field (Moro et al., 2006), the induced polarization of the cluster is determined by the orientational polarizability of the “rigid” cluster, rather than by the intracluster reorientation of the molecules. The calculated dependence of the effective polarizability of the cluster in the low field on n qualitatively reproduces the experimental results, but the calculated polarizability is numerically much higher than the experimental value by, e.g., a factor of 4 for n ≈ 20.     

Planar Droplet Sizing for the Characterization of Droplet Clusters in an Industrial Gun‐Type Burner

An important problem in spray combustion deals with the existence of dense regions of droplets, called clusters. To understand their formation mechanism, the droplet dynamics and fuel concentration profile are investigated by means of planar laser techniques in an industrial gun‐type burner. The simultaneous measurement of elastic Mie scattering and Laser Induced Fluorescence (LIF) allows the instantaneous measurement of the Sauter Mean Diameter (SMD), after proper calibration. Using two different CCDs to get the two signals requires a detailed calibration of the CCD response before getting absolute diameters. Pixels are binned 6 by 6 to obtain the final SMD map, this is a compromise between spatial accuracy and noise. Velocity field is measured on both sets of images using standard Particle Image Velocimetry (PIV) algorithms. The comparison of cross‐correlation technique with PDA results shows that the velocity measured on the LIF images are close to the velocity based on D₃₀, whereas the Mie scattering results are similar to D₂₀. On Mie scattering images, regions of high interfacial area forming clusters can be detected. A special tracking scheme is used to characterize their dynamics in terms of velocity and diameters by ensuring that the same volume of fluid is tracked. It is shown that the clusters have a velocity similar to the velocity of droplets with the same diameter as the mean SMD of the cluster. It is also shown that an increase of pressure tends to trigger the appearance of such a group of droplets, due to a smaller diameter of the droplets caused by the increase of pressure discharge. Uncertainties for the different techniques used are discussed.     

Ranges of implanted atoms under polyatomic cluster bombardment of the Cu (111) surface

A computer simulation of the bombardment of the Cu (111) surface with Cu_N and Au_N polyatomic clusters differing in size (N = 1, 6, and 13) with energies of 0.5 and 5 keV/atom has been performed in the framework of classical molecular dynamics. The spatial distribution of the implanted atoms, their ranges, and range fluctuations (straggling) depending on the size N and energy E/N of the incident cluster has been investigated. It has been shown that an increase in the mean range and range straggling is observed at a fixed energy per incident atom as the cluster size N increases. At the same time, the effect of an increase in the range (at a specified value of E/N) gradually disappears with increasing cluster energy, whereas the effect of an increase in straggling is retained. These tendencies qualitatively agree with the available experimental observations. It has been shown that the dominating contribution to the increase in the atom range of the implanted cluster is made by the so-called clearing-the-way effect, which is weakened with increasing the incident cluster energy. The effect of the range straggling increasing is significantly due to the presence of nonlinear “spike” effects at the bombarded target.     

Kinetic treatment of acoustic waves in a four‐component dusty plasma

A kinetic formulation is developed to investigate low‐frequency dust ion acoustic waves (DIAWs) and dust acoustic waves (DAWs) as well as numerically for a four‐component, collisionless, unmagnetized dusty plasma, using the linearized Vlasov–Poisson model for species obeying the Maxwellian distribution. In particular, the dynamics of low‐frequency DIAWs is investigated by considering two cases. In the first case, ions and positive dust particles are assumed to be dynamically adiabatic while the negative dust particles are static in the background. In second case, the ions are taken adiabatic, while both positive and negative dust particles are static in the background. For DAWs, the ions are assumed to be isothermal, while both positive and negative dust species are considered adiabatic. Electrons are assumed to be isothermal in all cases. The linear characteristics and Landau damping rates for DIAWs and DAWs are investigated with effects of the dust particle concentrations and different temperature ratios. It is noted that for higher values of positive dust concentration, DIAWs (DAWs) are less (more) damped. It is also observed that the damping rate increases (decreases) as T_i approaches T_e for DIAWs (DAWs). It is worth adding here that the theoretical results presented here are supported by numerical analyses and illustrations. The relevance of the study to laboratory and cosmic plasmas is also pointed out.     

Statistical mechanics of quantum spin systems

The thermodynamic limit of a quantum spin system is considered. It is demonstrated that for a large class of interactions and a wide range of the thermodynamic parameters the equilibrium state of the system is describable by an extremalZ ^v -invariant state (a single phase state) over aC* algebra of local observables. It is further shown that the equilibrium state may be obtained as the solution of a variational problem involving the mean entropy. These results extend results previously obtained for classical spin systems byGallavotti, Miracle-Sole andRuelle.     

On anomalous diffusion of fractal clusters under certain realistic physical conditions

Summary Diffusion of a fractal cluster of dimensiond _f in a three-dimensional space is investigated. The diffusion process is assumed to be modelled by a standard parabolic diffusion equation, although a more general case represented by the Fokker-Planck-Kolmogoroff equation is also introduced. The mean-square displacement of the cluster mass centre is analysed and its anomalous behaviour is presented and critically discussed. The results obtained can be applied to describe some effects which may occur during the diffusion-limited cluster-cluster aggregation process, especially when the viscosity of the solvent is changed in time and/or a directed transport of clusters is present in the system. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

染料敏化太阳电池中TiO2颗粒界面接触对电子输运影响的研究

采用溶胶-凝胶法制备TiO₂浆料,通过丝网印刷技术印刷和不同温度曲线烧结TiO₂薄膜,并应用于染料敏化太阳电池(DSC).高分辨透射电子显微镜发现,低温下多孔薄膜中TiO₂颗粒之间呈现点接触,510 ℃烧结后TiO₂颗粒间由点接触变为面接触,近邻颗粒数增多,接触面积增大.同时采用强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)技术,研究了不同颗粒接触方式和接触面积对电子传输与复合的影响.结果表明:在420- 510 ℃之间,随着烧结温度提高,颗粒接触面积增大,电子传输时间(τ _d)缩短,电子有效扩散长度(L _n)增大,暗电流减小;当烧结温度达到550 ℃时,薄膜比表面积减小,多孔结构坍塌,表面态密度增大,电子传输时间(τ _d)增大.电池光伏特性研究表明:在480-510 ℃范围内烧结得到的TiO₂薄膜,电池短路电流密度(J_sc)最佳,电池效率(η)最好. 关键词： 界面接触 电子输运 暗电流 染料敏化太阳电池