Shape-controlled crystallisation pathways in dense fluids of ccp-forming hard polyhedra

Emergent directional entropic forces that favour facet-to-facet alignment of neighbouring colloidal particles – arising from multi-body interactions upon crowding – should cause the process by which colloidal crystals form from fluids of hard polyhedra to be different than that from fluids of hard spheres. We compute nucleation-free energy barriers for a family of shapes that all self-assemble the same cubic close-packed (ccp) crystal structure formed by hard spheres and find that changing rhombicuboctahedra into rhombic dodecahedra by successively removing facets that compete with the ccp structure cause a systematic decrease in barrier heights. We show that this decrease arises from the increased prominence of facets aligned with neighbouring shapes in the target crystal, which produce local environments in the fluid that facilitate crystallisation.     

Normalisation and assessment of neutron diffraction data from liquids

A couple of normalisation criteria have been proposed to assess liquid structure data over the past decade. In this paper, a critical examination of these and other plausible criteria is made. Neutron diffraction data from liquid krypton measured by Clayton and Heaton is used to study these criteria. It is shown that if the structure factorS (Q)=1+γ (Q) satisfies the Krogh-Moe relation, namely whereQ is the wavevector transfer andρ ₀ the mean atomic number density,S (Q) is properly normalised. Subjecting such data to the other criteria would reveal, however, the quality of data in so far as systematic errors and/or termination errors are concerned. If the data is measured with reasonable accuracy to sufficiently large values of the wavevector transfer all these criteria would assess the quality of the data to almost the same extent. This is established in this paper by improving and extending the liquid krypton data by procedures similar to that of Kaplow, Strong and Averbach and subjecting this revised data to the various criteria. It is concluded, thereby, that (i) one can study the neutron diffraction data from liquids using any of the criteria mentioned in the paper to improve the quality of the data and (ii) for normalisation purposes the simple relation {ie328-2} would suffice.     

Phase behaviors of ionic liquids attributed to the dual ionic and organic nature

Ionic liquids (ILs), also known as room-temperature molten salts, are solely composed of ions with melting points usually below 100 °C. Because of their low volatility and vast amounts of species, ILs can serve as ‘green solvents' and ‘designer solvents' to meet the requirements of various applications by fine-tuning their molecular structures. A good understanding of the phase behaviors of ILs is certainly fundamentally important in terms of their wide applications. This review intends to summarize the major conclusions so far drawn on phase behaviors of ILs by computational, theoretical, and experimental studies, illustrating the intrinsic relationship between their dual ionic and organic nature and the crystalline phases, nanoscale segregation liquid phase, IL crystal phases, as well as phase behaviors of their mixture with small organic molecules.     

From mixing-demixing to condensation-evaporation phase transition in binary liquids

Summary Binary-fluid mixtures show first-order phase transition phenomena which are either classified as mixing-demixing (phase separation), or as condensation-evaporation. The localization of the transition lines, the characterization of the new phases, and the analysis of the parameters which force model systems to choose one of the two transition mechanisms is the aim of this study. We performed both parallel-molecular-dynamics simulations and integral-equation theory calculations on binary mixtures of Lennard-Jones particles. By fixing the composition and by varying the interaction strength, we found a continuous change between the two kinds of transition mechanisms. Theoretical and simulation results are compared with each other and a quantitative agreement i8s found. However, the simultation analysis appears to be more promising since, in contrast to the integral-equation theory in which the spinodal lines can only be approched, information on the microscopic structure of the new phases can be obtained. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copenello, Italy, July 4–8, 1994.     

On the memory functions in simple classical liquids

The relation between the two memory function formalisms for correlation functions in classical liquids is discussed. It is found that the kinetic equation formalism of Duderstadt and Akcasu with a simple exponential memory function can account for the double Gaussian form of the memory function in the generalized-hydrodynamics approach. The former therefore gives reasonably good results for the coherent scattering function S(k, ), as is shown for the case of liquid Rb at 315 K in the range 1.25 k 5.5 Å^–.     

Aggregates in mixtures of ionic liquids

Surfactant-like ionic liquids (C₁₆MIMCl, C₁₆MIMBF₄) aggregate in mixtures with another ionic liquid (EAN). Critical aggregate concentrations and estimations of object sizes are given and compared to aqueous systems and other relevant literature data. The investigated mixtures are stable up to more than 200 °C and can probably be used to extend the limited temperature range of water-based colloids.     

Structure, dsingle-particle and many-particle coefficients of Lennard—Jones liquid Al

We investigate the effects of temperature and density on the single-particle and many-particle coefficients as well as on the structures of homogenous systems in which the particles are assumed to interact via a continuous soft sphere potential in the microcanonical ensemble. The pair distribution function and therefore the structures of the systems studied are affected by temperature close to and above the melting point through migrations of atoms from the first shell in the pair distribution function. The dynamics of atomic pairs in the short-time regime in liquid aluminium may be said to be governed by the potential of mean force, which depends on the static structure of liquid Al at all investigated temperatures. A polynomial dependence ofD on density and temperature was observed in contradiction to Arrhenius law. The shear viscosities of the systems studied are largely nonlinear. It was observed that the soft sphere potential used in our calculations overestimates the Stoke-Einstein relation.     

Sonochemistry in non-aqueous liquids

The chemical effects of high-intensity ultrasound on organic liquids are reported. In order to probe the factors which affect sonochemistry in non-aqueous solvents, two very different chemical dosimeters have been used: radical trapping by diphenylpicrylhydrazyl and decomposition of Fe(CO)₅. In both cases, good correlation is found between the logarithm of the sonochemical rate and the solvent vapour pressure. This result is justifiable in terms of the cavitation ‘hot-spot’ mechanism of sonochemistry. Thus, decreasing solvent vapour pressure increases the intensity of cavitational collapse, the peak temperature reached during such collapse, and, consequently, the rates of sonochemical reactions.     

Review of the role of ionic liquids in two-dimensional materials

Ionic liquids (ILs) are expected to be used as readily available “designer” solvents, characterized by a number of tunable properties that can be obtained by modulating anion and cation combinations and ion chain lengths. Among them, its high ionicity is outstanding in the preparation and property modulation of two-dimensional (2D) materials. In this review, we mainly focus on the ILs-assisted exfoliation of 2D materials towards large-scale as well as functionalization. Meanwhile, electric-field controlled ILs-gating of 2D material systems have shown novel electronic, magnetic, optical and superconducting properties, attracting a broad range of scientific research activities. Moreover, ILs have also been extensively applied in various field practically. We summarize the recent developments of ILs modified 2D material systems from the electrochemical, solar cells and photocatalysis aspects, discuss their advantages and possibilities as “designer solvent”. It is believed that the design of ILs accompanying with diverse 2D materials will not only solve several scientific problems but also enrich materials design and engineer of 2D materials.     

金属液体结构与性能研究的新进展

金属液体的结构演化与其性能的关联一直都是凝聚态物理和材料科学领域的研究热点。文章介绍了金属液体结构的研究方法,以及液—液相变、物性参数和易碎性指数与其结构之间的内在关联性等基础科学问题的最新研究进展。随着金属液体结构和性能研究的不断深入,特别是大量先进实验方法的引入,加深了人们对金属液体的认识,同时促进了新材料的开发和性能改善等。     

A statistical-mechanical theory of self-diffusion in glass-forming liquids

A statistical-mechanical theory of self-diffusion in glass-forming liquids is presented. A non-Markov linear Langevin equation is derived from a Newton equation by employing the Tokuyama-Mori projection operator method. The memory function is explicitly written in terms of the force-force correlation functions. The equations for the mean-square displacement, the mean-fourth displacement, and the non-Gaussian parameter are then formally derived. The present theory is applied to the glass transitions in the glass-forming liquids to discuss the crossover phenomena in the dynamics of a single particle from a short-time ballistic motion to a long-time self-diffusion process via a β (caging) stage. The effects of the renormalized friction coefficient on self-diffusion are thus explored with the aid of analyses of the simulation results by the mean-field theory proposed recently by the present author. It is thus shown that the relaxation time of the renormalized memory function is given by the β-relaxation time. It is also shown that for times longer than the β-relaxation time the dynamics of a single particle is identical to that discussed in the suspensions.     

The influence of pressure on freezing in molecular liquids

We present the results of experimental investigation of some liquid alkanes PVT behaviour. Their molecular structure was investigated by MoK X-ray scattering method. The obtained data allow suggesting the equation of state and determination of the relation of these equation parameters to molecular characteristics such as molecular mass and exponents of the potential of molecular interaction.     

Neutron diffraction studies of simple molecular liquids

Summary A brief review is presented of the structural characteristics of diatomic and tetrahedral molecular liquids. Paper presented at the workshop ?Highlights on Simple Liquids?, held in Turin at ISI on 1–3 May, 1989.     

Onion-structured transition metal dichalcogenide nanoparticles by laser fabrication in liquids and atmospheres

Since the discovery of transition metal dichalcogenide (TMDC) nanoparticles (NPs) with the onion-like structure, many efforts have been made to develop their fabrication methods. Laser fabrication (LF) is one of the most promising methods to prepare onion-structured TMDC (or OS-TMDC) NPs due to its green, flexible, and scalable syntheses. In this mini-review article, we systematically introduce various laser-induced OS-TMDC (especially the OS-MoS₂) NPs, their formation mechanism, properties, and applications. The preparation routes mainly include laser ablation in liquids and atmospheres, and laser irradiation in liquids. The various formation mechanisms are then introduced based on the different preparation routes, to describe the formations of the corresponding OS-NPs. Finally, some interesting properties and novel applications of these NPs are briefly demonstrated, and a short outlook is also given. This review could help to understand the progress of the laser-induced OS-TMDC NPs and their applications.     

Tracer diffusion in glassforming liquids

In the last decades, a wide collection of experimental evidence has been found in the study of supercooled glassformers on the existence of a crossover between two dynamical regimes at a temperature T_c. We discuss the validity of the Vogel-Fulcher-Tammann in both regions. The breakdown of the Stokes-Einstein relation below T_c is presented, indicating that the diffusion coefficient of a tracer becomes decoupled from the viscosity through an exponent ξ, and the diffusion process is intensified. We verify that a temperature shift on the diffusion coefficient introduces the same effect as the Stokes-Einstein breakdown equation. We present the dependence of this exponent on the ratio between the radii of the tracer and the host liquid molecule.     

含气泡液体中气泡振动的研究

研究了含气泡液体中单个气泡在驱动声场一定情况下的振动过程. 让每次驱动声场作用的时间特别短, 使气泡半径发生微小变化后再将其变化反馈到气泡群对驱动声场的散射作用中去, 从而可以得到某单个气泡周围受气泡散射影响后的声场, 接着再让气泡在该声场作用下做短时振动, 如此反复. 通过这样的方法, 研究了液体中单个气泡的振动情况并对其半径变化进行了数值模拟, 结果发现, 在液体中含有大量气泡的情况下, 某单个气泡的振动过程明显区别于液体中只有一个气泡的情况. 由于大量气泡和驱动声场的相互作用, 使气泡半径的变化存在多种不同的振动情况, 在不同的气泡大小和含量的情况下, 半径变化过程分别表现为: 在平衡位置附近振荡的过程; 周期性的空化过程; 一次空化过程后保持某一大小振荡的过程; 增长后维持某一大小振荡的过程等. 所以, 对于含气泡液体中气泡振动的研究, 在驱动声场一定的情况下, 必须考虑气泡含量的因素. 关键词： 含气泡液体 超声空化 散射 数值模拟     

Equations of motion for rotational motion in liquids

The equations of motion corresponding to master equations describing rotational relaxation in liquids are shown to be purely deterministic and, in general, nonlocal in time.     

Raman spectra of acetonitrile in imidazolium ionic liquids

Raman spectra of dilute solutions of acetonitrile in ionic liquids reveal the characteristic features of ionic liquids' polarity. This is accomplished by investigating the Raman bandshape of the ν (CN) band, corresponding to the CN stretching mode of CH₃CN, which is a very sensitive probe of the local environment. The amphiphilic nature of the CH₃CN molecule allows us to observe the effect of electron pair acceptor and electron pair donor characteristics on ionic liquids. It has been found that the overall polarity of nine different ionic liquids based on 1‐alkyl‐3‐methylimidazolium cations is more dependent on the anion than cation. The observed wavenumber shift of the ν (CN) band of CH₃CN in ionic liquids containing alkylsulfate anions agrees with the significant different values previously measured for the dielectric constant of these ionic liquids. The conclusions obtained from the analysis of the ν (CN) band were corroborated by the analysis of the symmetric ν₁ (CD₃ ) stretching mode of deuterated acetonitrile in different ionic liquids. Copyright © 2010 John Wiley & Sons, Ltd.