Methane hydrate crystal growth in a porous medium filled with methane-saturated liquid water

The nucleation, growth and ageing of methane hydrate crystals were observed visually in a porous medium filled with liquid water presaturated with methane. The pore space dimensions of the porous medium were 1.0?×?10²?µm. The pressure?temperature conditions at which hydrate formation was initiated corresponded to system subcoolings of 3.4?K, 6.7?K, 12.3?K and 14.1?K, respectively, where the system subcooling denotes the difference of the system temperature from the triple methane?hydrate?water equilibrium temperature under a given pressure. Faceted (skeletal) hydrate crystals grew and bridged the pore spaces without intervention of a liquid water layer when the subcoolings were equal or smaller than 6.7?K. The faceted crystals may form a physical bonding with the walls of the porous medium. At the higher subcoolings, the dispersive formation of dendritic crystals and subsequent morphological change into particulate crystals were observed. The bridging of the dendritic crystals is unlikely in the absence of a large amount of additional methane supply due to the dispersive spatial distribution of the dendritic crystals that have dimensions smaller than those of the pore spaces. As a result of the interpretation of the observed variation in the crystal morphology of the methane hydrate formed in liquid water, the dependence of the crystal morphology on the magnitude of the mass transfer of methane molecules in liquid water observed in the porous medium was consistent with that previously observed in a bulk methane–water system.     

Dynamics and hydrogen bonding in liquid ethanol

Molecular dynamics simulations of liquid ethanol at three temperatures have been carried out. The hydrogen bonding states of ethanol molecules have been characterized by the number of hydrogen bonds in which the molecules participate. It is observed that the mean lifetimes of molecules in each hydrogen bonding state are markedly dependent on the temperature. Moreover, molecules with one hydrogen bond are more stable when they are donors than when they are acceptors. The dependence of the reorientational correlation functions on the hydrogen bonding state of molecules has been studied carefully. The decay of these functions is slower for molecules with higher numbers of hydrogen bonds and also becomes slower as temperature decreases. The relaxation for molecules with only one hydrogen bond is faster for those acting as proton donors than for those acting as proton acceptors. Finally, the results obtained by computer simulation are compared with those from recent measurements of the frequency-dependent dielectric permittivity of liquid ethanol.     

用分子动力学模拟甲烷水合物热激法分解

用分子动力学模拟方法研究甲烷水合物热激法分解，系统地研究注入340 K液态水的结构Ⅰ型甲烷水合物的分解机理.模拟显示水合物表层水分子与高温液态水分子接触获得热能，分子运动激烈，摆脱水分子间的氢键束缚，笼状结构被破坏.甲烷分子获得热能从笼中挣脱，向外体系扩散.热能通过分子碰撞从外层传递给内层水分子，水合物逐层分解.对比注入277K液态水体系模拟结果，得出热激法促进水合物分解. 关键词： 甲烷水合物 分子动力学模拟 热激法     

醇类抑制剂对甲烷水合物形成的影响

在本工作中,甲烷水合物的生长动力学是通过甲醇、乙醇、乙二醇三种不同醇类抑制剂存在下的分子动力学模拟研究的.模拟结果发现,三种醇类都可作为甲烷水合物的抑制剂,醇类分子中的亲水性羟基极大地破坏了水合物笼的结构,并且羟基可以与局部的液态水分子形成氢键,从而增加了形成水合物笼型结构的难度,导致甲烷水合物的生长速率降低.对于甲醇分子,甲醇分子的亲水性羟基与水分子形成氢键从而破坏了水分子结构,而亲油性甲基对周围的水分子具有簇效应,两者都会降低水合物生长速率;对于乙二醇和乙醇分子,它们只含有羟基,特别是乙二醇分子含有两个羟基,其对H₂O分子有很强的吸附作用,导致水合物生长速率降低.在抑制效果方面,甲醇分子最优,乙二醇稍微优于乙醇.     

Hydrogen-bond dynamics of interior and surface molecules in a water nanocluster: temperature and size effects

Molecular dynamics simulations are employed to investigate the effects of temperature and size on the hydrogen-bond dynamics of interior molecules and surface molecules in a water nanocluster. The flexible three-centred (F3C) water model is invoked in the simulations. To inspect the dynamics of the interior hydrogen bonds and the surface hydrogen bonds, a spherical water nanocluster is modelled and then divided into interior molecules and surface molecules according to the density profile of the water nanocluster. It is observed that at higher temperatures the average number of hydrogen bonds decreases and yields faster hydrogen-bond relaxation for both interior molecules and surface molecules of the water nanocluster. Furthermore, the surface molecules have a lower average number of hydrogen bonds than the interior molecules. The lifetime of the surface hydrogen bonds is slightly longer than that of the interior hydrogen bonds, whereas the hydrogen-bond structural relaxation time of the surface molecules is more obviously slower than that of the interior molecules. Regarding the size effect, a larger water nanocluster is seen to have a larger average number of hydrogen bonds and a longer hydrogen-bond structural relaxation time.     

用分子动力学模拟甲烷水合物热激法结合化学试剂法分解

用分子动力学模拟方法研究甲烷水合物的热激法，化学试剂法，以及热激法结合化学试剂法分解，系统研究温度为277K和340K时添加液态水(WTR)和30wt％乙二醇(EG)溶液对水合物分解的影响.模拟显示WTR与水合物表面水分子形成氢键，破坏水合物原有的氢键平衡，造成笼状结构坍塌，水合物分解.EG分子中的羟基与水合物表面水分子形成氢键，从而破坏原有的稳定结构，造成水合物笼状结构被破坏，达到促进水合物分解，释放甲烷气体的效果.比较温度为277K和340K时添加WTR和30wt％EG溶液对水合物分解效果得出EG(340K)> WTR(340K)>EG(277K)>WTR(277K)，热激法结合化学试剂法能更好促进水合物分解.     

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.     

X-ray emission spectroscopy of hydrogen bonding and electronic structure of liquid water

We use x-ray emission spectroscopy to examine the influence of the intermolecular interaction on the local electronic structure of liquid water. By comparing x-ray emission spectra of the water molecule and liquid water, we find a strong involvement of the a(1)-symmetry valence-orbital in the hydrogen bonding. The local electronic structure of water molecules, where one hydrogen bond is broken at the hydrogen site, is separately determined. Our results provide an illustration of the important potential of x-ray emission spectroscopy for elucidating basic features of liquids.     

Nuclear quantum effects in liquid water from path-integral simulations using an ab initio force-matching approach

We have applied path integral simulations, in combination with new ab initio based water potentials, to investigate nuclear quantum effects in liquid water. Because direct ab initio path integral simulations are computationally expensive, a flexible water model is parameterised by force-matching to density functional theory-based molecular dynamics simulations. Static and dynamic properties of liquid water at ambient conditions are presented and the role of nuclear quantum effects, exchange-correlation functionals and dispersion corrections are discussed in regards to reproducing the experimental properties of liquid water.     

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)].     

Structure of supercooled water in clusters and bulk and its relation to the two-state picture of water: Results from the TIP4P-ice model

The structure of water clusters (H₂O)_n (n = 40 -200) and bulk water were examined by molecular dynamics simulations using the TIP4P-ice water model. The analysis of the low-temperature structures in terms of the local structure index (LSI) showed a bimodal distribution. This finding supports the two-state picture derived from the analysis of the inherent dynamics of bulk SPC/E water. The water molecules at the outer interface of the coldest clusters are more structured than those in the inner core. The geometrical constraint of the interface forces the surface molecules to lose one neighbor and adopt a local angular distribution of hydrogen bonds resembling that found in the basal plane of ice Ih.     

Collective Effect of Transformation of a Hydrogen Bond Network at the Initial State of Growth of Methane Hydrate

JETP Letters - The molecular dynamics study of the rearrangement of the dynamic hydrogen bond network of liquid water to the crystal hydrogen bond network of methane hydrate in the process of their...     

Recent experimental aspects of the structure and dynamics of liquid and supercooled water

Liquid water, the most familiar liquid, is still not completely understood, even less so all the processes in which it participates. The directionality of the bonds and quantum aspects make the establishment of a complete theory difficult, particularly in the case of effective potentials built with spherical electrostatic forces. Recent work has focused on the hydrogen bonds formed between water molecules or with hydrophilic substrates. We describe the present situation of research concerning the so-called anomalies of liquid water at low temperature. Although without direct applications, this problem is consistently an object of discussion, enhanced by results from molecular dynamics simulations. Conversely, because in many situations where water plays a major role, such as, for example, in biology, only a few molecules are involved, the study of confined water is extremely important, sometimes decoupled from the more fundamental studies of bulk water. A short, but far from exclusive, summary of some of the more active domains of research concerning liquid water is given, mainly concerning interactions with other media.     

Oxide/water interfaces: how the surface chemistry modifies interfacial water properties

The organization of water at the interface with silica and alumina oxides is analysed using density functional theory-based molecular dynamics simulation (DFT-MD). The interfacial hydrogen bonding is investigated in detail and related to the chemistry of the oxide surfaces by computing the surface charge density and acidity. We find that water molecules hydrogen-bonded to the surface have different orientations depending on the strength of the hydrogen bonds and use this observation to explain the features in the surface vibrational spectra measured by sum frequency generation spectroscopy. In particular, 'ice-like' and 'liquid-like' features in these spectra are interpreted as the result of hydrogen bonds of different strengths between surface silanols/aluminols and water.     

Influence of thermal treatment on the dynamics of the Goldstone mode in ferroelectric liquid crystal gel

ABSTRACT

Broadband dielectric spectroscopy was applied to investigate the effect of gel-former agent on the dynamics of the collective modes in a ferroelectric liquid crystal mixture. In the investigated range of gel concentrations, the dynamics of the Goldstone mode is significantly reduced due to the formation of a hydrogen bonding network of the gel-former agent in ferroelectric liquid crystal. The observed changes in dynamics of the collective processes are sensitive to the history of the thermal treatment of the samples.     

Water Dynamics at Interfaces and Solutes: Disentangling Free Energy and Diffusivity Contributions

The dynamics of single water molecules in bulk and at interfaces is studied by means of molecular dynamics simulations. We use a recently developed stochastic method based on the Fokker-Planck equation to disentangle the contributions of the free energy and diffusivity profiles on the local dynamics. The strong variations found in the diffusivity profiles are crucial for accurately modeling the water kinetics. A comparison of hydrophobic and hydrophilic substrates and solutes yields significant differences in the diffusivities, which can be attributed to the presence of hydrogen bonds.     

A molecular level study of liquid water with a flexible water model

The structural properties of water at different temperatures and pressures have been investigated by using a flexible water model and the inherent structure mechanism. The presence of 60$^\circ$ peak in the O--O--O angle distribution function and the behaviours of the hydrogen bonds in the first shell indicate that some water molecules in the second shell move toward the central molecules through the bending (not breaking) of hydrogen bonds and even become first-shell molecules of the central molecule on the basis of the O--O cutoff distance but not first-shell molecules by means of the hydrogen-bond criterion. The inherent-structure analysis of the O--O radial distribution functions at different pressures shows that the first peak is almost independent of the pressure; the position of second peak moves from 0.45 to 0.32nm as the pressure increases from $1\times 10^5$Pa to $1\times 10^9$Pa. This particularly evident pressure effect, i.e. the constant nearest-neighbours and the transformation of outer-neighbours on the basis of O--O distance, together with the results at different temperatures, gives a positive evidence for the two-state outer-neighbour mixture model: liquid water is a mixture of Ice-Ih-type-bonding and Ice-II-type bonding structures.     

Resolving the optical spectrum of water: coordination and electrostatic effects

The optical absorption of small water clusters, water chains, liquid water, and crystalline ice is analyzed computationally. We identify two competing mechanisms determining the onset of the optical absorption: Electronic transitions involving surface molecules of finite clusters or chains cause a redshift upon molecular aggregation compared to monomers. On the other hand, a strong blueshift is caused by the electrostatic environment experienced by water monomers embedded in a hydrate shell. Concerning the recent dispute over the structure of the liquid, the present results support the conventional fourfold coordinated water, as obtained from ab initio molecular-dynamics simulations.     

Atomistic simulations of liquid water using Lekner electrostatics

Equilibrium molecular dynamics simulations have been performed for liquid water using three different potential models in the NVT and NPT ensembles. The flexible SPC model, the rigid TIP4P model and the rigid/polarizable TIP4P-FQ potential were studied. The Lekner method was used to handle long range electrostatic interactions, and an efficient trivariate cubic spline interpolation method was devised for this purpose. A partitioning of the electrostatic interactions into medium and long range parts was performed, and the concomitant use of multiple timestep techniques led to substantially enhanced computation speeds. The simulations were carried out using 256 molecules in the NVT ensemble at 25°C and 997 kg m^?3 and in the NPT ensemble at 25°C and 1 bar. Various dynamic, structural, dielectric, rotational and thermodynamic properties were calculated, and it was found that the simulation methodologies performed satisfactorily vis-à-vis previous simulation results and experimental observations.     

Dynamical and structural properties of adsorbed water molecules at the TiO2 rutile-(110) surface: interfacial hydrogen bonding probed by ab-initio molecular dynamics

ABSTRACT

Ab-initio molecular dynamics (AIMD) simulations have been carried out to study a range of different and energetically-accessible adsorbed-water configurations and motifs for their vibrational and structural characteristics, in contact with rutile-(110) interfaces at 100?K. The radial pair distribution function between the titanium atoms at the interface and the hydrogen and oxygen atoms in the water monolayer show an orientation of the water molecules parallel to the surface of titania, and with hydrogen atoms pointed in the opposite direction to the surface. In some cases, a distinctive vibrational frequency region between 2500 and 3000?cm^?1 has also been observed, due to a strong dispersion interaction between water molecules. This behaviour is also seen in experimental studies of thin-film water coverage on TiO₂ surfaces.