分子动力学模拟方解石和白云石润湿性

利用分子动力学模拟研究油水分子在方解石和白云石表面的吸附,分析体系的平衡构型、相对浓度、径向分布函数和吸附能,研究方解石和白云石的亲水性并对比二者差异.根据油水分子吸附规律分析方解石/白云石-油水体系作用机理.研究表明：白云石-油水体系更易达到热力学稳定状态并且体系更加稳定;方解石和白云石表面均能够优先吸附水分子并在表面形成双层结构的水膜.其中,白云石表面对水分子吸附强度大于方解石;稳定吸附过程分为两步：范德华力、静电力和O（CaCO₃,CaMg（CO₃）₂）-H（H₂O）氢键共同影响下水分子向晶体表面移动并吸附形成紧密吸附层;O（H₂O）-H（H₂O）氢键作用下游离的H₂O向晶体表面靠近形成扩散层.从分子尺度解释方解石/白云石亲水特性,为碳酸盐岩储层润湿性研究奠定理论基础.     

Structure and Dynamics of Ethanol Adsorbed on a Mica Surface

The structural and dynamic properties of nanoscale ethanol film on a mica surface are investigated via molecular dynamics simulations.We observe a dense,almost flat ethanol bilayer formed in the vicinity of the mica surface,with the hydrophobic alkyl groups pointing outward from the surface.Remarkably,such ethanol bilayer is laterally well-ordered with patterned adsorption sites.Each ethanol molecule in the first layer donates one hydrogen bond to the surface basal oxygen atoms and accepts one hydrogen bond from that in the second layer.The ethanol molecules within the bilayer exhibit constrained lateral mobility and delayed dynamics as compared with bulk ethanol,whereas those on top of the bilayer have bulk-like characteristics.     

The influence of substrate temperature on growth of para-sexiphenyl thin films on Ir{111} supported graphene studied by LEEM

The growth of para-sexiphenyl (6P) thin films as a function of substrate temperature on Ir{111} supported graphene flakes has been studied in real-time with Low Energy Electron Microscopy (LEEM). Micro Low Energy Electron Diffraction (μLEED) has been used to determine the structure of the different 6P features formed on the surface. We observe the nucleation and growth of a wetting layer consisting of lying molecules in the initial stages of growth. Graphene defects – wrinkles – are found to be preferential sites for the nucleation of the wetting layer and of the 6P needles that grow on top of the wetting layer in the later stages of deposition. The molecular structure of the wetting layer and needles is found to be similar. As a result, only a limited number of growth directions are observed for the needles. In contrast, on the bare Ir{111} surface 6P molecules assume an upright orientation. The formation of ramified islands is observed on the bare Ir{111} surface at 320 K and 352 K, whereas at 405 K the formation of a continuous layer of upright standing molecules growing in a step flow like manner is observed.     

Study of glucose oxidase–l-α-lecithin Langmuir film formation on air–water interface

The present paper describes the formation of glucose oxidase (GOx)–l-α-lecithin Langmuir film on air–water interface by spreading GOx solution directly onto subphase covered with layer of lecithin. The optimum experiment conditions were obtained according to the experimental results. Two phase transition processes were observed under surface pressure ranges of 8.0–11.0 mN/m and 15.0–30.0 mN/m, which represented the movement of GOx molecules under the lecithin layer and the reorientation of GOx molecules in the lecithin layer and/or expulsion of GOx molecules from the lecithin layer, respectively. The forces of GOx molecules that interacted with the lecithin layer were hydrogen bonding and hydrophobic force. An atomic force microscopy image of GOx–lecithin film deposited on Au (1 1 1) surface in optimal conditions gives evidence of well-ordered GOx molecules in the lecithin layer. As a target of this research, this work provides a new way to prepare biomimetic film and design glucose biosensors in future.     

Investigation of the local structure variance of water molecules in laser-induced thermal desorption process

This paper presents the use of molecular dynamics simulation in the study of laser-induced thermal desorption (LITD) of water molecules adjacent to a laser-heated Au substrate. The local structure of the water molecules is investigated by considering the densities of the oxygen and hydrogen atoms, the average number of neighbors, n_NN, and the average number of H-bonds, n_HB. At an equilibrium temperature of 300 K, the simulation results show that three adsorption water layers are formed in the immediate vicinity of the Au surface, and that each four-fold hollow site on the uppermost Au(0 0 1) surface is occupied by a single water molecule. Following laser-induced heating of the Au substrate with a sub-picosecond laser pulse of 350 fs, the substrate temperature increases to 1000 K. This causes a gradual heating of the adjacent water film, which is accompanied by a decrease in the values of n_NN and n_HB. Hence, it can be concluded that an increase in the water film temperature destroys the hydrogen-bonding network throughout the water film. Although the maximum local temperature of the water film occurs in the region immediately adjacent to the Au substrate, it is determined that the attractive energy between the Au atoms and the water molecules in this region causes the water molecules to aggregate together to form three-dimensional water clusters. Furthermore, this energy prevents the hydrogen bonds in this region from breaking apart as violently as those within the phase explosion region. Finally, it is observed that the phase explosion phenomenon occurs in the region of the water film where the values of n_NN and n_HB are at a minimum.     

界面氢键对受限水结构和动态特性的影响

应用反应力场分子动力学方法, 模拟了水限制在全羟基化二氧化硅晶体表面间的弛豫过程, 研究了基底表面与水形成的界面氢键, 及其对受限水结构和动态特性行为的影响. 当基底表面硅醇固定时, 靠近基底表面水分子中的氧原子与基底表面的氢原子形成强氢键, 这使得靠近表面水分子中的氧原子比对应的氢原子更靠近基底表面, 从而水分子的偶极矩远离表面. 当基底表面硅醇可动时, 靠近基底表面水分子与基底表面原子形成两种强氢键, 一种是水分子中的氧原子与表面的氢原子形成的强氢键, 数量较少, 另一种是水分子中的氢原子与表面的氧原子形成的强氢键, 数量较多, 这使得靠近表面水分子中的氢原子比对应的氧原子更靠近表面, 从而水分子的偶极矩指向表面. 在相同几何间距下, 当基底表面硅醇可动时, 表面的活动性使得几何限制作用减弱, 导致了受限水分层现象没有固定表面限制下的明显. 此外, 固定表面比可动表面与水形成的界面氢键作用较强, 数量较多, 导致了可动表面限制下水的运动更为剧烈.     

Enhancement of water self-diffusion at super-hydrophilic surface with ordered water

It has been well acknowledged that molecular water structures at the interface play an important role in the surface properties, such as wetting behavior or surface frictions. Using molecular dynamics simulation, we show that the water self-diffusion on the top of the first ordered water layer can be enhanced near a super-hydrophilic solid surface. This is attributed to the fewer number of hydrogen bonds between the first ordered water layer and water molecules above this layer, where the ordered water structures induce much slower relaxation behavior of water dipole and longer lifetime of hydrogen bonds formed within the first layer.     

Hydrophobicity-induced drying transition in alkanethiol self-assembled monolayer—water interface

During the course of our investigation of the electron transfer properties of some redox species through highly hydrophobic long chain alkanethiol molecules on gold in aqueous and non-aqueous solvents, we obtained some intriguing results such as unusually low interfacial capacitance, very high values of impedance and film resistance, all of which pointed to the possible existence of a nanometer size interfacial gap between the hydrophobic monolayer and aqueous electrolyte. We explain this phenomenon by a model for the alkanethiol monolayer—aqueous electrolyte interface, in which the extremely hydrophobic alkanethiol film repels water molecules adjacent to it and in the process creates a shield between the monolayer film and water. This effectively increases the overall thickness of the dielectric layer that is manifested as an abnormally low value of interfacial capacitance. This behaviour is very much akin to the ‘drying transition’ proposed by Lum, Chandler and Weeks in their theory of length scale dependent hydrophobicity. For small hydrophobic units consisting of apolar solutes, the water molecules can reorganize around them without sacrificing their hydrogen bonds. Since for an extended hydrophobic unit, the existence of hydrogen bonded water structure close to it is geometrically unfavourable, there is a net depletion of water molecules in the vicinity leading to the possible creation of a hydrophobic interfacial gap.     

Langmuir-Blodgett film and nematic interface

The orientation induced by a Langmuir-Blodgett film on a Nematic Liquid Crystal (NLC) is theoretically analyzed. We show that the effective surface energy is due to different contributions connected with steric and van der Waals interactions between the nematic and the solid substrate. The analysis shows that the Langmuir-Blodgett film orientation depends on the surface density of the molecules. The initial homeotropic orientation may become unstable giving rise to a tilted film. The average orientation of the nematic molecules is also analyzed. We show that, in the event in which the steric interaction Nematic-Langmuir-Blodgett film is very large with respect to the dispersion interaction Nematic-Substrate, the nematic orientation coincides with the one of the film. On the contrary, when the two interactions are comparable, the orientation of the two media may differ. In particular, we analyze how the stable orientation depends on the surface molecular density of the film.     

Effect of iron doping on the hydrophobicity of titanium dioxide film: experiment and simulation

In this study, we carried out experiments and molecular dynamics simulations to identify the effect of Fe doping on the hydrophobicity of a titanium dioxide film. TiO₂ and Fe-doped TiO₂ films were fabricated in situ by atomic layer deposition without annealing. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to characterise the crystal structure and elemental composition. Iron doping resulted in the TiO₂ becoming more hydrophobic at a macroscopic level, as estimated by atomic force microscopy observations and static contact angle measurements. Furthermore, the effect of iron doping on the structure and kinetics of water molecules on the exterior of TiO₂ were studied by molecular dynamics simulations. On the basis of the XPS results, the Fe-TiO₂ surface matrix has a Ti:Fe ratio of 36:5. In addition, the density distribution of oxygen and hydrogen atoms indicate that interfacial water molecules enter the Fe-TiO₂ film more easily and hydrogen atoms in the water molecules are oriented upward at the interface. The self-diffusion coefficients indicate that iron doping makes the TiO₂ more hydrophobic, which is consistent with the macroscopic test results.     

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     

Aqueous electrolyte surfaces in strong electric fields: molecular insight into nanoscale jets and bridges

Exposing aqueous surfaces to a strong electric field gives rise to interesting phenomena, such as formation of a floating water bridge or an eruption of a jet in electrospinning. In an effort to account for the phenomena at the molecular level, we performed molecular dynamics simulations using several protocols on both pure water and aqueous solutions of sodium chloride subjected to an electrostatic field. All simulations consistently point to the same mechanisms which govern the rearrangement of the originally planar surface. The results show that the phenomena are primarily governed by an orientational reordering of the water molecules driven by the applied field. It is demonstrated that, for pure water, a sufficiently strong field yields a columnar structure parallel to the field with an anisotropic arrangement of the water molecules with their dipole moments aligned along the applied field not only in the surface layer but over the entire cross section of the column. Nonetheless, the number of hydrogen bonds per molecule does not seem to be affected by the field regardless of its strength and molecule’s orientation. In the electrolyte solutions, the ionic charge is able to overcome the effect of the external field tending to arrange the water molecules radially in the first coordination shell of an ion. The ion–water interaction interferes thus with the water–electric field interaction, and the competition between these two forces (i.e., strength of the field versus concentration) provides the key mechanism determining the stability of the observed structures.     

Investigation of the adsorption mechanism of water nanocluster on the substrate: The size and interaction strength effect

Molecular dynamics simulation is utilized to investigate the effects of both the size of a water nanocluster and the interaction strength between the water nanocluster and a solid surface on the dynamic behavior of the water nanocluster when it is adsorbed on a solid surface. The simulation results demonstrate that both the size and the interaction strength influence the adsorption behavior of the water nanocluster on the substrate. When the interaction strength between water molecules and the substrate is strong, the morphology of the water nanocluster adsorbed on the substrate will tend to be flatter in shape. However, when the interaction strength is weak, the morphology of the water nanocluster is a semi-spherical shape. The size of the water nanocluster causes the water molecules in the first layer to lay flatter on the substrate at stronger interaction strengths. As the interaction strengths exceed 1.5 kcal mol⁻¹, the value of orientation factor will reverse its trend for water nanoclusters with different sizes, with the smaller water nanocluster having the smallest orientation factor.     

ATR-SEIRAS--an approach to probe the reactivity of Pd-modified quasi-single crystal gold film electrodes

Quasi-single crystalline gold films of 20 nm thickness and preferential (1 1 1) orientation on Si hemispheres were modified by controlled potentiostatic deposition of Pd (sub-ML, ML, multi-L) from sulphate and/or chloride-containing electrolyte. The electrochemical properties of these model electrodes were characterised for hydrogen and (hydrogen-) sulphate adsorption as well as for surface oxide formation by cyclic voltammetry. Conditions were developed to fabricate defined and stable Pd monolayers. In situ ATR-SEIRAS (Attenuated Total Reflection Surface Enhanced Infrared Reflection Absorption Spectroscopy) experiments were carried out to describe the electrochemical double layer of Pd modified gold film electrodes in contact with aqueous 0.1 M H₂SO₄ with focus on interfacial water and anion adsorption. Based on an analysis of the non-resonant IR background signal the potential of zero charge is estimated to 0.10-0.20 V (vs. RHE). CO was found to be weakly physisorbed in atop sites on Au(1 1 1-20 nm)/0.1 M H₂SO₄ only in CO saturated electrolyte. CO, deposited on a quasi-single crystal gold film modified with 1 ML Pd, is chemisorbed with preferential occupation of bridge sites and atop positions at step edges. Saturated CO adlayers, as obtained by deposition at 0.10 V, contain isolated water species and are covered by a second layer of hydrogen bonded water. Potentiodynamic SEIRAS experiments of CO electro-oxidation on Pd-modified gold film electrodes demonstrate clearly the existence of a “pre-oxidation” region. They also provide spectroscopic evidence that isolated water and weakly hydrogen bonded water are consumed during the reaction and that atop CO on defect sites is a preferential reactant. The simultaneous in situ monitoring of the potential- and time-dependent evolution of characteristic vibrational modes in the OH- and CO-stretching regions are in agreement with the Gilman (“reactant pair”) mechanism of CO oxidation.     

Molecular adsorption and growth of naphthalene films on Ag(1 0 0)

The adsorption of naphthalene, vacuum deposited on a Ag(1 0 0) surface, was comprehensively investigated by means of low-energy electron diffraction (LEED), temperature-programmed thermal desorption (TPD) spectroscopy, X-ray photoelectron spectroscopy (XPS), and polarization-dependent near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in the mono- and multilayer regime. A growth of long-range ordered monolayer at 140 K is observed with LEED. The polarization-dependent C 1s NEXAFS shows that the naphthalene molecules in the monolayer lie almost parallel to the Ag(1 0 0) surface. With increasing film thickness, the molecular orientation turns to upright position. Furthermore, NEXAFS measurements show that in the multilayer regime the molecular orientation depends on the substrate temperature during deposition.     

Adsorption of short-chain alkanethiols on Ag(1 1 1) studied by direct recoiling spectroscopy

We use direct recoiling spectroscopy with time-of-flight analysis to study the adsorption of propanethiol on Ag(1 1 1) cleaned and polished in vacuum by cycles of grazing ion bombardment and annealing. We discuss the advantages and drawbacks of the technique to follow the growth of the organic film. In particular, the low damage imparted by the technique allows to follow in detail the evolution of the H, C and substrate recoiling peaks for a wide range of exposures ranging from 10⁻¹ to 2 × 10⁴ L. The shape of the TOF spectra and the evolution of the recoiling intensities are consistent with a growth process in three stages: an initial fast one related to the density of defects at the surface, a second one where the surface is covered with a thin layer of organic molecules, presumably associated with lying-down molecules, and a final stage corresponding to a thicker layer that can be associated with a standing-up orientation of the molecules in the film. Annealing of the organic film to 250 °C produces complete depletion of C and H, leaving a small amount of S. The final S coverage after annealing depends on the initial roughness, being higher for rougher surfaces. We also observe an increase in the surface roughness after desorption of the thiol layer. Re-adsorption on this post annealed surface presents a marked enhancement of the initial sticking.     

Increase in the hydraulic pressure in various zones of a two-fluid hydrophilic capillary due to nonuniformity of the external electric field

The phenomenon whereby the thickness of the water film next to the inner surface of a hydrophilic capillary filled with two fluids increases in the presence of an external static electric field is investigated. A hypothesis of the essential nature of the phenomenon is submitted, along with a corresponding equation for calculating numerically the thickness variations as a function of several parameters of the working system, including the strength of the external field. Experimental results are given. The results of theoretical calculations and the experimental data are shown to be in good agreement. The orientation of stationary dipoles of the molecules constituting highly polar liquids in an electric field is estimated. Zh. Tekh. Fiz. 68, 24–30 (August 1998)     

石墨烯表面的特征水分子排布及其湿润透明特性的分子动力学模拟

石墨烯因其独特的分子构型、卓越的物理化学性能而受到广泛关注.本文首先利用分子动力学模拟比较了单层石墨烯、铜、二氧化硅三者表面的浸润性,除了接触角的比较,还分析了基底表面的水分子排布,得到石墨烯表面的特征水分子排布为:表面有两层密集的水分子层,其中靠近基底的密集水分子层中O—H键与垂直基底方向夹角集中在90°附近,并且基底表面的氢键几乎都垂直于基底.另一方面,本文研究了石墨烯浸润透明特性,发现在铜和二氧化硅上添加一层石墨烯,对铜的浸润性影响较小,对二氧化硅的浸润性影响很大,不仅使其上接触角显著增大,还使得基底表面的水分子排布呈现出类似单层石墨烯上的规律.本文使用分子动力学模拟方法从微观尺度验证了文献的实验结果,从基底表面水分子排布角度分析了石墨烯独特的浸润透明特性,为进一步开发石墨烯在微结构设计上的应用提供了理论指导.     

卟啉基非金属纳米片用于可见光光催化制氢

本文基于密度泛函理论预测了一种用于可见光范围光催化制氢的新型二维非金属纳米材料,该材料可以由HTAP分子脱氢聚合得到,具有良好的结构稳定性,且带隙为2.12 eV,可以实现可见光区域的光捕获. 材料的带边能级位置恰好包裹水的氧化还原电位,有利于实现全光解水. 电子的迁移率略高于空穴的迁移率,有利于光生载流子的分离. 光生电子可以提供足够的驱动力使得析氢反应自发进行.     

How polar hydroxyl groups affect surface hydrophobicity on model talc surfaces

Based on molecular dynamics simulations, we have studied the wetting behaviors of water on the talc-like surface with different surface polarity by modifying the charge distribution of surface hydroxyl (–OH) groups. With the change of the charge of the hydrogen atom (denoted as δ_q) in –OH group, the contact angle decreases from 91° to 50° and then remains constant. On the surfaces with the larger charge of hydrogen atoms (δ_q ≥ 0.2 e), a water droplet is formed above a water monolayer, which is exactly contacted on the surface. Each water molecule in the monolayer forms one hydrogen bond (H bond) with surface –OH groups, without participating in any H bond with the water molecules within the monolayer or with the water molecules above the monolayer. The polarity of the –OH group also has a great influence on the dynamic behaviors of the interface water, such as residence time, hydrogen bond lifetime and self-diffusion coefficient. The diffusion of water molecules in the water monolayer near the highly polar surface is greatly suppressed, and the residence time of water molecules in the water monolayer even exceeds 12 ns.