The performance of non-polarizable and polarizable force-field parameter sets for ethylene glycol in molecular dynamics simulations of the pure liquid and its aqueous mixtures

Non-polarizable and polarizable force-field parameter sets for liquid ethylene glycol (EG) were developed for use in biomolecular simulation. In the polarizable models, electronic polarization effects were explicitly taken into account using the charge-on-spring method. The quality of the new force fields and two non-polarizable EG models taken from the literature was investigated by calculating relevant properties of the pure liquid and its aqueous mixtures, and comparing simulation results with experimental data. The performance of the EG models as a co-solvent in aqueous mixtures was additionally evaluated in a hydrophobic hydration study. The question was whether the experimentally known maximum in the solvation free enthalpy of argon at intermediate mixture compositions could be reproduced in the simulations. Values for the dielectric properties and excess free energy were found to be more off from experiment for the polarizable models than for the non-polarizable ones. However, a Kirkwood–Buff analysis of the aqueous mixtures and the hydrophobic hydration results exemplified that electronic polarization plays an important role in correctly describing attractive interactions between the EG and water co-solvent molecules. The trans/gauche ratio for ethylene glycol's O–C–C–O torsional angle was not found to systematically affect the properties of the pure liquid and aqueous mixtures.     

微秒脉冲下碳酸丙烯酯的击穿特性

采用紧凑Tesla变压器型脉冲功率驱动源及球电极击穿试件,通过改变初级充电电压,开展了微秒级充电条件下碳酸丙烯酯及其与碳酸乙烯酯的混合液的击穿实验研究。由结果和分析可知:碳酸丙烯酯理论工作温度可低至-55℃,这意味着它可以成为一种低温下的良好液体电介质;碳酸丙烯酯耐压性能与去离子水相当,且实测电阻率达到了10 MΩ·cm以上;向碳酸丙烯酯中添加碳酸乙烯酯后,介电常数可提高至80以上,耐压强度也有所提升;将碳酸丙烯酯、碳酸乙烯酯/碳酸丙烯酯混合液用于脉冲形成线作为储能介质无需附加去离子处理系统,有利于装置的紧凑化和小型化。     

A one-site polarizable model for liquid chloroform: COS/C

A one-site polarizable liquid chloroform model based on the charge-on-spring method is presented. It consists of five van der Waals sites and point charges, with one polarizable center on the carbon atom. The partial charges were adjusted to fit the gas-phase dipole moment of chloroform, and the Lennard–Jones parameters were varied to reproduce the density and the heat of vapourization of liquid chloroform. In this way, a simple polarizable model for liquid chloroform was obtained that correctly describes a variety of its thermodynamic, dynamic and dielectric properties, while the computational costs are only a factor of 2 higher than for a similar non-polarizable chloroform model. The model is simpler than two previously developed polarizable chloroform models, with four or five polarizable sites. The developed COS/C model is expected to show realistic behaviour of chloroform molecules in response to changes in electric field strength or the dielectric environment and should be applicable in simulations of biomolecules in conjunction with the GROMOS biomolecular force field.     

Density functional theory calculations for ethylene carbonate-based binary electrolyte mixtures in lithium ion batteries

The density functional theory (DFT) calculations have been performed to investigate the interaction of Li⁺ with various organic solvents widely used as Li ion rechargeable battery electrolytes such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC); and their EC-based binary mixtures at the level of B3LYP/6-31G (d). The interaction of Li⁺ with these solvents has been calculated in terms of electronic structures of clusters of the mixtures of organic solvents including a lithium ion. The main objective of our investigation is to help in understanding a stable and enhancing ionic transfer at graphite/electrolyte interface assisted by the mixtures of the solvents. The calculated results favor the stability of EC-based binary mixtures and high EC-content binary mixture systems. In infrared (IR) vibrational spectra, the IR active modes of the solvent show significant changes due to the cation-solvent interaction.     

碳酸二甲酯与柴油混合物粘度的实验研究

利用密度瓶和玻璃毛细管粘度计,本文对293~353 K温度范围内的碳酸二甲酯与柴油混合物的密度与粘度进行了实验研究,得到了不同配比下碳酸二甲酯与柴油混合物的密度与粘度实验数据。利用得到的实验数据,拟合了不同配比下的碳酸二甲酯与柴油混合物的密度与粘度计算方程。根据Grunberg-Nissan方法,最终得到了混合物粘度的计算方程,此方程适用于碳酸二甲酯的比例不超过20％的情况,分析表明计算结果与实验数据的偏差小于5％,可以满足工程实际应用的需要。     

Identification of accidentally degenerate bands in UV photoelectron spectra of ethylene carbonate and propylene carbonate

High resolution photoelectron spectra of ethylene carbonate and propylene carbonate were taken, and analysis of vibrational structures was made for the     

聚合物及其混合物的太赫兹介电性质测定与分析方法

聚合物材料因其对太赫兹波的高透过率以及良好的塑形能力在太赫兹研究中扮演了重要的角色,由于材料的介电特性直接关系着折射率、极化率等重要性质,不同的应用场合通常需要材料呈现出特殊的太赫兹介电响应,一方面可以选取不同的聚合物材料,另一方面可以通过多种聚合物的混合实现材料介电性质的调制。聚合物材料合理的选取和设计建立在材料太赫兹介电精确表征之上,然而利用太赫兹时域光谱系统(THz-TDS)对聚合物材料进行透射式太赫兹介电表征时,材料内部空气孔隙的存在会影响表征结果的复现性,同时也会影响共混聚合物介电性质的分析和预测。因此以Landau, Lifshitz, Looyenga(LLL)模型为基础提出了考虑空气影响的介电分析模型,并选取了在太赫兹研究中广泛使用的聚合物材料聚乙烯(PE)和聚四氟乙烯(PTFE)对模型的有效性和稳定性加以验证,展开了两种材料单质和混合物两方面的介电分析。在太赫兹波透射样品之后的相位变化信息中提取出样品的介电常数,同一种物质制备的样片间太赫兹介电谱存在明显差异,使用包含气隙影响的LLL模型处理实验数据后,样品介电常数中空气的介电影响被移除,从而得到了两种材料的本征介电常数,在此基础上,使用测得的本征介电常数和混合物样品中两种材料的体积占比信息代入包含气隙影响的LLL模型计算得到了不同配比混合物的太赫兹介电常数的模拟值,并与THz-TDS实验获取的实验值进行了对比。利用所提出的有效介质模型,聚乙烯和聚四氟乙烯在10～40 cm-1波段内移除空气影响后的平均介电常数为2.315±0.003（±0.13%）和2.109±0.003（±0.14%）,在不同重量、不同厚度的单组份样品间模型测定的聚合物介电常数保持了良好的重复性,在对混合物的太赫兹介电性质测定与分析中,利用模型计算的混合物介电常数模拟值与THz-TDS测定的介电常数实验值保持了高度线性相关,其相关系数为0.964 3,全局相对误差为1.08%,体现了模型的可靠性。提出的介电分析模型可以扩展到更多的高分子材料单质及其混合物的太赫兹介电性质表征中,对太赫兹波段的共混聚合物材料设计具有参考价值。     

Potential of mean force for ion pairs in non-aqueous solvents. Comparison of polarizable and non-polarizable MD simulations

Potentials of mean force (PMF) are calculated for two model ion pairs in two non-aqueous solvents. Standard non-polarizable molecular dynamics simulation (NPMD) and approximate polarizable simulation (PMD) are implemented and compared as tools for monitoring PMF profiles. For the polar solvent (dimethylsulfoxide, DMSO) the PMF generated in terms of the NPMD reproduces fairly well the refined PMD–PMF profile. For the non-polar solvent (benzene) the conventional NPMD computation proves to be deficient. The validity of the correction found in terms of the approximate PMD approach is verified by its comparison with the result of the explicit PMD computation in benzene. The shapes of the PMF profiles in DMSO and in benzene are quite different. In DMSO, owing to dielectric screening, the PMF presents a flat plot with a shallow minimum positioned in the vicinity of the van der Waals contact of the ion pair. For the benzene case, the observed minimum proves to be unexpectedly deep, which manifests the formation of a tightly-binded contact ion pair. This remarkable effect arises owing to the strong electrostatic interaction that is incompletely screened by a non-polar medium. The PMFs for the binary benzene/DMSO mixtures display intermediate behaviour depending on the DMSO content.     

Toughening of Propylene‐ethylene Copolymer/Calcium Carbonate Composites with High‐Density Polyethylene

Propylene‐ethylene copolymer/calcium carbonate (CaCO₃) composites (weight ratio=50/50) toughened with high density polyethylene (HDPE) were prepared using a twin‐screw extruder; the HDPE content in composites was in the range of 0–4 wt.%. The notched impact strength of propylene‐ethylene copolymer/CaCO₃ composites with 1.5 wt.% HDPE was 46% higher than that of propylene‐ethylene copolymer/CaCO₃ composites. Differential scanning calorimetry (DSC) experiments showed that good miscibility between propylene‐ethylene copolymer and HDPE enhanced the interpenetration of the macromolecules located in the interface. It was shown that debonding of the small HDPE particles within the propylene‐ethylene copolymer matrix resulted in the formation of small voids; the subsequent plastic deformation of the propylene‐ethylene copolymer matrix next to the voids thinned the ligaments and led to large energy consumption.     

Electro-optic and dielectric behavior of a FLC material having doped with a non-mesogenic polar molecules

Liquid crystal mixtures of non-mesogenic polar molecule with a commercial ferroelectric liquid crystal (FLC) mixture were prepared. Two mixtures were prepared by mixing 0.5% (w/w) and 1% (w/w) of polar molecules with commercial FLC mixture. Comprehensive studies of dielectric and electro-optic properties of the commercial FLC mixture and the polar molecules doped FLC mixtures have been made as a function of temperatures. Our studies reveal a higher tilt angle in lower concentration (0.5%) mixture but in case of 1% mixture tilt angle is decreased in comparison to 0.5% mixture. The spontaneous polarization of the commercial FLC mixture and other two mixtures is almost equal in magnitude at all temperatures. At the lower temperature region of SmC¹ phase, Goldstone mode (GM) dielectric strength of the commercial FLC mixture and low concentration (0.5%) mixture is found almost equal but it is slightly higher in case of high concentration (1%) mixture. With the increase of temperature GM dielectric strength of both the doped mixtures rapidly converges at different temperatures which are much lower than the temperature of transition (T_C) from SmC¹ – SmA phase. The results have been discussed.     

Measurement and modeling of the sooting propensity of binary fuel mixtures

The sooting behaviour of binary fuel mixtures was evaluated both experimentally and through computer simulations. The soot volume fraction in laminar diffusion flames of mixtures of ethylene/propane, methane/ethylene, methane/propane, methane/ethane, methane/butane, ethane/propane and ethane/ethylene fuels was measured using 2-dimensional line of sight attenuation. A synergistic effect was observed for the ethylene/propane, methane/ethylene, methane/ethane and ethane/ethylene mixtures. The synergistic effect translated into a higher soot concentration for a mixture fraction than could be yielded by the added contribution of both pure fuels. Such an effect was not observed for the methane/propane, methane/butane and ethane/propane mixtures. Through experiments in which the flame temperature was kept constant, it was determined that the synergistic effect in the methane/ethylene mixture is very temperature dependent whereas, that in the ethylene/propane mixture is not. This phenomenon was further studied through the modeling of the ethylene/propane mixture. Numerical simulations were carried out using two different soot models. The simulations confirmed the presence of a synergistic effect. It was found that the effect could be directly correlated to a synergistic effect in the concentration of n-C₄H₅ and n-C₄H₃, which could be traced back to an interaction between ethylene and methyl radical species. These results yield further insight into the pathways to soot formation and highlight the importance of further analyzing binary fuel mixtures as a means of understanding soot formation in practical devices using industrial fuels.     

Raman study of lithium coordination in EMI‐TFSI additive systems as lithium‐ion battery ionic liquid electrolytes

Raman spectroscopy was performed on various mixtures of the ionic liquid salt, 1‐ethyl‐3‐methylimidazolium‐bis(trifluoromethylsulfonyl)imide (EMI‐TFSI). When EMI‐TFSI is used in combination with a lithium salt, it could be a potential electrolyte for lithium‐ion or lithium metal batteries. The Raman spectra of EMI‐TFSI, EMI‐TFSI 0.5 M Li‐TFSI, EMI‐TFSI 0.5 M Li‐TFSI 2 M vinylene carbonate (VC) and EMI‐TFSI 0.5 Li‐TFSI 2 M ethylene carbonate (EC) were collected and compared. A comparison of the peak positions of the δ_s CF₃ mode at 742 cm⁻¹ demonstrates that when carbonate additives are present, the lithium ion is no longer interacting with the TFSI anion. Instead, it is coordinated with the carbon–oxygen double bond of the carbonates. Copyright © 2006 John Wiley & Sons, Ltd.     

Calculation of the vapour-liquid coexistence curve for a fluctuating point charge water model

Recent studies of the phase behaviour of several polarizable water models have shown that typically the inclusion of polarizability into current non-polarizable, rigid models of water actually decreases the accuracy of their predictions of the liquid-vapour coexistence curve. Most of the polarizable models examined so far have been shown to characteristically over-predict the saturation pressure and correspondingly under-predict the critical temperature. It is the purpose of this Research Note to report the results of a Gibbs—Duhem integration of the liquid—vapour coexistence curve for the TIP4P-FQ water model and to discuss the possible reasons behind the lack of improvement of polarizable water models over their non-polarizable counterparts.     

Theory and simulation of electrolyte mixtures

Monte Carlo simulation and theoretical results on some aspects of thermodynamics of mixtures of electrolytes with a common species are presented. Both charge symmetric mixtures, where ions differ only in size, and charge asymmetric but size symmetric mixtures at ionic strength ranging generally from I = 10^?4 to 1.0 M, and in a few cases up to I = 2 M, are examined. The theoretical methods explored are: (i) the symmetric Poisson-Boltzmann theory, (ii) the modified Poisson-Boltzmann theory and (iii) the hypernetted-chain integral equation. The first two electrolyte mixing coefficients w ₀ and w ₁ of the various mixtures are calculated from an accurate determination of their osmotic pressure data. The theories are seen to be consistent among themselves, and with certain limiting laws in the literature, in predicting the trends of the mixing coefficients with respect to ionic strength. Some selected relevant experimental data have been analysed and compared with the theoretical and simulation trends. In addition the mean activity coefficients for a model mimicking the mixture of KC1 and KF electrolytes are calculated and hence the Harned coefficients obtained for this system. These calculations are compared with the experimental data and Monte Carlo results available in the literature. The theoretically predicted Harned coefficients are in good agreement with the simulation results for the model KC1-KF mixture.     

Broadband dielectric spectroscopy on glass-forming propylene carbonate

Dielectric spectroscopy covering more than 18 decades of frequency has been performed on propylene carbonate in its liquid and supercooled-liquid state. Using quasioptic submillimeter and far-infrared spectroscopy, the dielectric response was investigated up to frequencies well into the microscopic regime. We discuss the alpha process whose characteristic time scale is observed over 14 decades of frequency and the excess wing showing up at frequencies some three decades above the peak frequency. Special attention is given to the high-frequency response of the dielectric loss in the crossover regime between alpha peak and boson peak. Similar to our previous results in other glass-forming materials, we find evidence for additional processes in the crossover regime. However, significant differences concerning the spectral form at high frequencies are found. We compare our results to the susceptibilities obtained from light scattering and to the predictions of various models of the glass transition.     

Static dielectric properties of polarizable Stockmayer fluids

The effect on the thermodynamics and distribution functions in including point polarizability in the Stockmayer fluid is evaluated. A large effect on the dielectric constant is found. As in the non-polarizable case, the single super chain integral equation gives dielectric constants in excess of the computed values except at low dielectric constants.     

The C Chemical Shift Tensor Principal Values and Orientations in Dialkyl Carbonates and Trithiocarbonates

The ¹³C chemical shift tensor principal values for the trigonal carbonate and thiocarbonate carbon atoms in the dialkyl carbonates, dimethyl carbonate, ethylene carbonate, and diphenyl carbonate, and in the trithiocarbonates, ethylene trithiocarbonate and dimethyl trithiocarbonate, respectively, were measured in various solid-state one-dimensional and two-dimensional nuclear magnetic resonance experiments. Furthermore, the chemical shift tensor principal values and orientations were calculated for the corresponding isolated molecules with quantum mechanically fully optimized geometries. Proton-optimized X-ray geometries of ethylene carbonate, ethylene trithiocarbonate, and diphenyl carbonate were used in embedded ion method (EIM) calculations and in calculations on the isolated molecules to obtain the theoretical principal values and to assign the chemical shift tensor orientations in these three compounds. Considerable improvement in the correlation between the experimental and calculated principal values is obtained when the electrostatic crystal potentials are included in EIM calculations. The chemical shift tensor orientations and principal values obtained for the dialkyl compounds in this study complement the previous data on a series of ionic potassium carbonates and thiocarbonates.     

Fluids of polarizable hard spheres with dipoles and tetrahedral quadrupoles Integral equation results with application to liquid water

The mean spherical, linearized hypernetted chain and quadratic hypernetted chain approximations are solved for a fluid of hard spheres with embedded point dipoles and tetrahedral quadrupoles and this system is shown to be quite similar to the dipole-linear quadrupole case previously studied. However, tetrahedral quadrupoles have a larger influence upon the structural and thermodynamic properties and are slightly more effective in decreasing the dielectric constant from the purely dipolar value. Also we describe a simple self-consistent mean field theory which allows molecular polarizability to be taken into account. This approximation together with the integral equation methods is applied to a polarizable dipole-tetrahedral quadrupole fluid with water-like parameters. The dielectric constant of this system is found to be in good agreement with the experimental results for liquid water for temperatures ranging from 25°C to 300°C. The influence of molecular polarizability is shown to be very large. At 25°C the mean dipole moment is ～2·56 D compared with ～1·85 D in the gas phase and the dielectric constant increases from ～25 for non-polarizable particles to ～80 for the polarizable model.     

The 13C chemical shift tensor principal values and orientations in dialkyl carbonates and trithiocarbonates

The 13C chemical shift tensor principal values for the trigonal carbonate and thiocarbonate carbon atoms in the dialkyl carbonates, dimethyl carbonate, ethylene carbonate, and diphenyl carbonate, and in the trithiocarbonates, ethylene trithiocarbonate and dimethyl trithiocarbonate, respectively, were measured in various solid-state one-dimensional and two-dimensional nuclear magnetic resonance experiments. Furthermore, the chemical shift tensor principal values and orientations were calculated for the corresponding isolated molecules with quantum mechanically fully optimized geometries. Proton-optimized X-ray geometries of ethylene carbonate, ethylene trithiocarbonate, and diphenyl carbonate were used in embedded ion method (EIM) calculations and in calculations on the isolated molecules to obtain the theoretical principal values and to assign the chemical shift tensor orientations in these three compounds. Considerable improvement in the correlation between the experimental and calculated principal values is obtained when the electrostatic crystal potentials are included in EIM calculations. The chemical shift tensor orientations and principal values obtained for the dialkyl compounds in this study complement the previous data on a series of ionic potassium carbonates and thiocarbonates.     

The Effects of Charge Transfer Interactions on the Properties of Ice Ih

Potential models which include charge transfer are used to study ice/water coexistence properties and properties of the ice Ih phase. Two charge transfer models are used, one which is non-polarizable and one which is polarizable. These models transfer a discreet amount of charge for each hydrogen bond made and the net charge of a molecule is determined by the difference in the number of hydrogen bonds a molecule makes as a donor and as an acceptor. In ice Ih, this difference is very near zero and the net amount of charge transfer is correspondingly essentially zero. This differs from the amount of charge transfer in the liquid phase. The results for the polarizable charge transfer model confirm other studies that suggest the importance of polarizability in reproducing the high dielectric constant of ice Ih.