Theoretical study of the permeation of water through TiO2 nanotubes using molecular dynamics simulation

In this study, the theoretical structures of armchair (6, 6) and zigzag (12, 0) TiO₂ nanotubes (TiNTs) were constructed by rolling the (101) layer of an anatase TiO₂ crystal. The (101) layer was made using Materials Studio (MS) by cutting the cleave plane (101) of the anatase TiO₂ crystal. Based on these structures, the basic properties of TiO₂ nanotubes were investigated using MS. Molecular dynamics simulations were performed using the software NAMD to investigate the status and permeation of water through the TiO₂ nanotubes. Structure analysis shows that both the inner and outer walls of the structures were terminated with oxygen atoms. The thicknesses of single tube walls are smaller than that of a perfect triple layer (2.20?Å) in bulk anatase TiO₂. With regard to the bulk Ti–O bond length, the Ti–O bonds in the outer layer are elongated, and are shortened in the inner layer. Molecular dynamics simulation shows that the water molecules in the nanotubes move back and forth, as in one-dimensional Brownian motion. Moreover, the penetration properties of TiNTs are associated with their radii, with the TiNT with larger radii having better penetration properties. Thus, when used in drug delivery or filtration systems, armchair TiNT has a better effect than zigzag TiNT.     

Ionic liquids in external electric and electromagnetic fields: a molecular dynamics study

The non-thermal effects of external electric and electromagnetic fields in the microwave to far-infrared frequency range and at (r.m.s.) electric field intensities of 10^?3 to 0.25?V/Å_r.m.s. on neat salts of 1,3-dimethyl-imidazolium hexafluorophosphate ([dmim][PF₆]) and 1-butyl-3-methyl-imidazolium hexafluorophosphate ([bmim][PF₆]) have been investigated by means of non-equilibrium molecular dynamics simulation. Significant alterations in molecular mobility were found vis-à-vis zero-field conditions. Using Green–Kubo and transient time correlation function analysis, the electrical conductivity of these ionic liquids has been estimated. The results indicate that ionic liquids respond most significantly to frequencies much lower than those of smaller polar solvents such as water, although the mechanism of the field response is almost exclusively translational.     

Molecular dynamics simulation of the response of bi-disperse polyelectrolyte brushes to external electric fields

Langevin dynamics simulations have been performed to investigate the response of bi-disperse and strong polyacid chains grafted on an electrode to electric fields generated by opposite surface charges on the polyelectrolyte(PE)-grafted electrode and a second parallel electrode. Simulation results clearly show that, under a negative external electric field, the longer grafted PE chains are more strongly stretched than the shorter ones in terms of the relative change in their respective brush heights. Whereas under a positive external electric field, the grafted shorter chains collapse more significantly than the longer ones. It was found that, under a positive external electric field, the magnitude of the total electric force acting on one shorter PE chain is larger than that on one longer PE chain, or vice versa. The effects of smeared and discrete charge distributions of grafted PE chains on the response of PE brushes to external electric fields were also examined.     

The role of external electric fields in membrane-based separation processes: a molecular dynamics study

Molecular simulations using the method of molecular dynamics have been carried out to determine if external fields can be used to increase the efficiency of membrane-based separation processes, examining both direct and several alternating electric fields, and across a range of frequencies. The results show that alternating electric fields have considerable promise as a valuable, yet generally neglected, tool for improving the efficiency of otherwise difficult separation processes.     

Classical dynamics of polar diatomic molecules in external fields

In this paper, we present the study of the global classical dynamics of a rigid diatomic molecule in the presence of combined electrostatic and nonresonant polarized laser fields. In particular, we focus on the collinear field case, which is an integrable system because the z-component P_φ of the angular momentum is conserved. The study involves the complete analysis of the stability of the equilibrium points, their bifurcations and the evolution of the phase flow as a function of the field strengths and P_φ. Finally, the influence of the bifurcations on the orientation of the quantum states is studied.     

Relativistic quantum dynamics of a neutral particle in external electric fields: An approach on effects of spin

The planar quantum dynamics of a spin-1/2 neutral particle interacting with electrical fields is considered. A set of first order differential equations is obtained directly from the planar Dirac equation with nonminimum coupling. New solutions of this system, in particular, for the Aharonov–Casher effect, are found and discussed in detail. Pauli equation is also obtained by studying the motion of the particle when it describes a circular path of constant radius. We also analyze the planar dynamics in the full space, including the r=0$r=0$ region. The self-adjoint extension method is used to obtain the energy levels and wave functions of the particle for two particular values for the self-adjoint extension parameter. The energy levels obtained are analogous to the Landau levels and explicitly depend on the spin projection parameter.     

The effect of external electric fields on molecular liquids and induced translational motion

A computer simulation is reported of the enantiomer S CHBrClF subjected in the liquid state to intense external fields of force : i) uniaxial electric field E_Z; ii) circularly polarised field at optical frequencies. The molecular dynamics are quantified in detail at field - on equilibrium in case i) using a range of auto correlation functions. The foremost result of the investigation is that the simple uniaxial field E_Z makes the sample $\text{translate}$ in a well defined direction. The direct effect of E_Z on an isolated molecule of S-CHBrClF is purely rotational, but intramolecular rotation/translation coupling converts this rotation into coherent centre of mass translation. This gives rise to direct, $\text{laboratory frame}$, cross correlations of the type <v(t)$\text{J}$^T(o)> where $\text{v}$ is the molecular centre of mass translational velocity and $\text{J}$^T the transposed molecular angular momentum vector. (The existence of these invalidates the classical theory of the Kerr effect.) The molecular dynamics of the hypothetical chiral ion S-CHBrClF^? are looked at with a view to corroborating the predictions by Baranova et al. concerning their response to electric field treatment. Despite the inherent instability of such an ensemble of like-charged ions the simulation can be used to produce a range of auto and cross-correlation functions with which to characterise the ionic dynamics. The effect of treating the ionic ensemble with a field E_Z is reported briefly in terms of the non-vanishing ensemble averaged centre of mass velocity <v_Z&>;.The induced translation in an electric field may be demonstrated on most liquids using a simple experimental set up. Its importance in optically active systems is such that it may be used to separate a racemic mixture into its enantiomers, the translational motion induced in the one enantiomer is necessarily, by symmetry, opposite to that induced in the other enantiomer. The observation therefore has technological importance. Other applications are discussed.     

Sorption and permeation of gaseous molecules in amorphous and crystalline PPX C membranes: molecular dynamics and grand canonical Monte Carlo simulation studies

Amorphous and crystalline poly (chloro-p-xylylene) (PPX C) membranes are constructed by using a novel computational technique, that is, a combined method of NVT+NPT-molecular dynamics (MD) and gradually reducing the size (GRS) methods. The related free volumes are defined as homology clusters. Then the sorption and the permeation of gases in PPX C polymers are studied using grand canonical Monte Carlo (GCMC) and NVT-MD methods. The results show that the crystalline PPX C membranes provide smaller free volumes for absorbing or transferring gases relative to the amorphous PPX C area. The gas sorption in PPX C membranes mainly belongs to the physical one, and H bonds can appear obviously in the amorphous area. By cluster analyzing on the mean square displacement of gases, we find that gases walk along the x axis in the crystalline area and walk randomly in the amorphous area. The calculated permeability coefficients are close to the experimental data.     

Symmetry effects of electric and magnetic fields in liquid state molecular dynamics

It Is shown that ensemble averages in molecular liquids may be investigated using group theoretical methods. These my he applied both in the laboratory frame (X,Y,Z) and the frame of the principal molecular moments of inertia (x,y,z). Using these methods the effect of an external electric field () and external magnetic field ( ) may be considered in terms of second order quantities such as the single molecule cross correlation function (t) ^T(o) where is the molecular centre of mass linear velocity and the angular velocity of the same molecule. Group theory, applied in this way, confirms the recent discovery by computer simulation of non-vanishing elements of (t) ^T(o) in frame (X,Y,Z) in the presence of an electric field. Group theory predicts, however, that these elements vanish in the presence of a magnetic field, even though this produces alignment and birefringence through the Langevin function. This leads to a straightforward experimental method for the direct observation of the non-vanishing elements of (t) ^T(o).     

Relaxation dynamics and power spectra of liquid water: a molecular dynamics simulation study

We present molecular dynamics simulations of liquid water at normal and supercooled conditions. Autocorrelation functions (ACFs) of several structural quantities and their fourier transforms are obtained and analysed. Structural correlations and relaxation times increase linearly with degree of supercooling. Power spectra of ACFs show increase in librational motion of liquid water with cooling. These modes intensify with supercooling because of structuring and ordering of water molecules. Overall, liquid water structure is homogenous over the temperatures and pressures studied and undergoes fluctuation–dissipation in its local-density variations [English and Tse, Phys. Rev. Lett. 106, 037801 (2011)].     

广义等温等压系综-分子动力学模拟全原子水的气液共存形貌

探测相变过程中瞬时共存相的形貌等特征对理解其微观机制十分重要.本文应用广义等温等压系综-分子动力学模拟方法,研究全原子水模型的气液两相平衡及相变的中间过程.研究发现,此广义系综方法能够通过持续降温,连续地历经从气态、气液共存到液态的整个相变过程,通过持续升温历经其相反过程,而不会发生标准正则系综中的过饱和热滞现象.该方法不需要使用副本交换等增强抽样方法,因此可以用于较大体系的研究,多个独立的模拟即能获得整个气态液态区的平衡性质及共存相特征.本文还提出了计算气液共存界面面积的新方法,给出了水的气液共存界面形状随温度、压强的变化规律.结果表明,低压时水的气液共存界面因其较大的表面张力而接近球面,符合经典成核理论的描述,但随着压强升高接近其临界压强时,气态和液态的差别减小,界面的表面张力变小,界面形状变为无规则的枝杈结构,表现为二阶相变特征.     

Heterogeneous crystallization of amorphous silicon expedited by external force fields: a molecular dynamics study

Applying a molecular dynamics simulation technique with the Tersoff potential, we investigate the isothermal crystallization processes of amorphous silicon (a-Si). To obtain a realistic amorphous structure, a rapid quenching process from liquid-phase at 3500 K to solid-phase at 500 K is simulated at a rate of 10¹² K/s and the Voronoi analysis is conducted to observe atomic structural changes during this cooling process. This amorphous structure is utilized to simulate the crystallization processes at various process temperatures with and without external force fields. While homogeneous crystallization of a-Si could not be achieved readily, it is shown that the heterogeneous crystallization can be significantly accelerated by external force fields. This enhancement is owing to increased molecular jumping frequencies associated with the molecular potential energies being increased by external excitations, rather than due to thermal mechanisms normally found in conventional solid-phase crystallization processes.     

A molecular dynamics simulation of the destruction of explosive molecules at high-velocity collisions

The infrared spectra and the energies of dissociation of R-NO₂ bonds (R≡C, N, and O) were calculated for explosive molecules (trinitrotoluene, hexogen, octogen, pentaerythrityl tetranitrate, triaminotrinitrobenzene, and nitromethane). The time of kinetic energy redistribution over intramolecular vibrational modes for these molecules (the V-V relaxation time) was calculated by the molecular dynamics simulation method. Molecular dynamics simulations were also used to model the collision-induced destruction of hexogen, octogen, and tri-nitrotoluene molecules. The threshold velocities of collisions at which the destruction of molecules took a time shorter than the V-V relaxation time were determined.     

High-resolution spectroscopy on trapped molecular ions in rotating electric fields: A new approach for measuring the electron electric dipole moment

High-resolution molecular spectroscopy is a sensitive probe for violations of fundamental symmetries. Symmetry violation searches often require, or are enhanced by, the application of an electric field to the system under investigation. This typically precludes the study of molecular ions due to their inherent acceleration under these conditions. Circumventing this problem would be of great benefit to the high-resolution molecular spectroscopy community since ions allow for simple trapping and long interrogation times, two desirable qualities for precision measurements. Our proposed solution is to apply an electric field that rotates at radio frequencies. We discuss considerations for experimental design as well as challenges in performing precision spectroscopic measurements in rapidly time-varying electric fields. Ongoing molecular spectroscopy work that could benefit from our approach is summarized. In particular, we detail how spectroscopy on a trapped diatomic molecular ion with a ground or metastable ³Δ₁ level could prove to be a sensitive probe for a permanent electron electric dipole moment (eEDM).     

Saturated sodium chloride solution under an external static electric field: A molecular dynamics study

The behavior of saturated aqueous Na Cl solutions under a constant external electric field(E) was studied by molecular dynamics(MD) simulation. Our dynamic MD simulations indicated that the irreversible nucleation process towards crystallization is accelerated by a moderate E but retarded or even prohibited under a stronger E, which can be understood by the competition between self-diffusion and drift motion. The former increases with E, thereby accelerating the nucleation process, whereas the latter pulls oppositely charged ions apart under a stronger E, thereby decelerating nucleation.Additionally, our steady-state MD simulations indicated that a first-order phase transition occurs in saturated solutions at a certain threshold Ec. The magnitude of Ec increases with concentration because larger clusters form more easily when the solution is more concentrated and require a stronger E to dissociate.     

Force fields for molecular dynamics simulation of the deposition of a silicon dioxide film

In this work we compare two force fields that are intended for the molecular dynamics simulation of the process of the deposition of silicon dioxide thin films. Analysis of the structural characteristics (the density and radial distribution function) of a glassy silicon dioxide cluster that was used as a substrate and a deposited film is carried out. It is shown that the DESIL force field in which the Van der Waals interaction is described by the Lennard–Jones potential turns out to be more suitable for modeling the process of deposition.     

外电场下交联聚乙烯电介质材料分子结构变化及其电老化微观机理研究

为了从微观角度分析交联聚乙烯(XLPE)材料的电树枝老化,本文采用分子模拟方法计算并优化得到了XLPE分子结构.沿着聚乙烯链施加不同大小电场强度,分析交联聚乙烯分子的几何结构、偶极矩、极化率、电荷分布、前线轨道能量和红外光谱变化规律.计算结果表明,随着外电场的增大,交联聚乙烯分子红外光谱发生较大变化;当外施电场达到0.026a.u.后,红外光谱图中出现虚频,表明分子空间结构不再稳定,易发生断键;另外从前线轨道图的变化可以看出断键现象最先发生在交联聚乙烯链端部;沿着电场方向,原子所带电荷量由交联处向端部转移,当外施电场达到0.029a.u.后,链端部的C-H和C-C键断裂产生H·和CH_3·自由基.游离的自由基会形成空间电荷并发生积聚,产生局部较大场强,从而进一步影响交联聚乙烯链的空间结构.而电介质内部微观特性的变化必定会导致交联聚乙烯材料绝缘性能的下降,这些变化对揭示交联聚乙烯电缆电树枝形成的微观规律具有重要研究意义.