Ⅰ型甲烷水合物晶体稳定性的分子动力学模拟

采用分子动力学方法,模拟了晶穴占有率和温度变化对I型甲烷水合物晶体稳定性的影响。通过考察晶体破坏过程中最终构象、均方位移、扩散系数、径向分布函数等分子的动力学和结构性质的变化,分析了分子动力学模拟中晶体结构失稳的微观特征,并提出了判断甲烷水合物晶体结构失稳的依据,这对水合物形成和分解过程的研究具有重要的参考价值。     

分子动力学模拟温度变化对I型甲烷水合物稳定性的影响

在单晶胞体系下,采用分子动力学的方法,利用搭建的势能模型,模拟了温度的变化对Ⅰ型甲烷水合物晶体稳定型的影响。通过分析不同温度下水合物晶体的径向分布函数、势能函数以及压力函数图像,得出了在水合物形成及分解过程中,温度越低,水合物势能越小、压力的波动性越小,晶体结构的稳定性也就会越好。该结论为以后水合物的形成和分解过程的研究提供了重要的参考依据。     

基于温度对H型水合物稳定性影响的分子动力学模拟

采用分子动力学模拟平台(ME),计算了H型水合物的性质及结构参数,并通过分析水合物晶体的最终构像、径向分布函数、均方位移、扩散系数、模拟体系势能等微观特征参数,考察了温度对H型水合物晶体结构稳定性的影响。模拟结果表明,随温度的升高,H型水合物的稳定性降低,笼型结构有分解之趋势。     

分子动力学模拟HEWL晶体在不同环境中的动力学行为

简要阐述分子动力学模拟的原理及步骤,介绍研究溶菌酶的一般方法和优缺点。在Ubuntu操作系统环境下,利用Gromacs软件和其自带的Gromos96力场,通过分子动力学模拟(MD)鸡蛋清溶菌酶晶体(chicken egg-whitelysozyme,HEWL)溶液,考察真空、水溶液和加入NaCl 3种不同环境条件对溶菌酶晶体构象动力学行为的影响,发现无论从均方根位移(rmsd)、回旋半径、还是从B因子值的轨迹图分析,HEWL在水溶液特别是加入抗衡离子(Na~+,Cl~-)的水溶液的环境下的结构更稳定、合理,与(protein data bank)数据库的真实情况相符。原因是Cl~-与溶菌酶晶体在界面处发生了吸附现象,局部形成溶菌酶-Cl~-复合物,抑制了蛋白-水合物中水分子在相邻水合位置间的跳跃,从而使单晶体在离子液态中更加稳定。模拟结果表明,在pH值6.5,等电位点13.1,总电荷7.999 6的体系下,影响HEWL的吸附位点为123号残基(色氨酸),对从分子水平上解释HEWL晶体的动力学吸附行为具有重要指导意义。     

基于CT的含水合物沉积物电阻率测量系统设计与开发

为满足从微观尺度研究沉积物孔隙中水合物分布对电阻率响应特性影响的需求,设计开发了基于CT的含水合物沉积物电阻率测量系统,包括天然气水合物实验模拟部分、电阻率测量部分和CT扫描部分,实现了水合物原位生成过程中电阻率和CT扫描图像的同时监测。通过开展甲烷水合物生成实验,验证了系统的可用性。实验结果表明：（1）电阻率随通过CT图像计算的水合物饱和度呈指数规律上升;（2）水合物饱和度为17.13%~30.72%时,阿尔奇公式中饱和度指数在1.57至2.48之间。所开发的测量系统为进一步开展不同环境条件下水合物生成分解实验提供了技术保障,为研究水合物微观分布对电阻率的影响以及优化水合物饱和度计算模型提供了数据支撑。     

分子动力学模拟蛋白质溶液吸附过程构象的变化

计算机模拟作为一种工具在药物分子设计、蛋白质工程、药物筛选等方面逐渐广泛应用起来。为了从分子水平上理解蛋白质吸附的机理，本文采用了刚体模型对聚十赖氨酸在固体表面吸附进行了分子动力学模拟。采用立方周期性边界条件，模拟在NVT条件下进行，各刚体的起始速度按Maxwell取样。初步研究了模拟过程中蛋白质构象的变化，跟踪了吸附过程中二面角φ和ψ的变化。研究结果表明，吸附过程中蛋白质二级结构发生了变化，C末端二级结构的变化最为明显。     

多孔介质中天然气水合物二维模拟实验装置

本文介绍了一种天然气水合物模拟实验装置,该装置能模拟多孔介质中天然气水合物的生成和分解过程.能够通过测量平板内探针的电容判断水合物的状态变化.实践证明,该装置工作稳定可靠,性能符合实验要求.     

高压可视化天然气水合物实验装置的研究

对高压可视化天然气水合物实验装置进行了研究.实验装置以现有天然气水合物开采方法结合水合物法海水淡化技术为研究背景,模拟海洋环境;利用水合物技术原位制备热盐水,开采海洋天然气水合物;采用可视化技术,可观察到水合物晶体状态.实际应用表明,该装置达到了设计效果,同时还可以应用到海水淡化等领域.     

纳米薄膜面向导热系数的分子动力学模拟

基于分子动力学研究纳米薄膜的导热系数现状,建立了一种导热模型.采用非平衡态分子动力学研究了纳米薄膜长度、厚度、空穴对导热系数的影响.选取结构简单、可靠实验数据和势能函数的晶体氩为模型,计算了氩晶体薄膜面向导热系数.模拟结果表明:纳米薄膜面向导热系数随薄膜长度和厚度增加而增加,增加到一定尺寸时,不再增加,近似相等,具有显著的尺寸效应.相同条件下,存在空穴的氩晶体纳米薄膜导热系数低于理想氩晶体纳米薄膜的导热系数.     

天然气水合物试验装置的智能化设计

介绍了一种天然气水合物实验研究装置，该装置能模拟水合物的生成和开采过程。系统工作稳定，性能完全符合实验要求，自动化程度高，为研究水合物提供了基本保证。     

Molecular potential energies in dodecahedron cell of methane hydrate and dispersion correction for DFT

The interaction potential energies of water-water and water-methane in structure-I unit cell of methane hydrate are calculated from 2.1 to 8.0A using density functional theory (DFT) B3LYP/TZVP. The curves of potential energies are corrected for basis set superposition error (BSSE) and dispersion interaction using a 4-term L-J (4,6-8,12) correction equation, which is derived from CCSD(T)/cc-pVTZ calculations of water-water and water-methane molecular pairs, using least squares curve-fitting. The methane hydrate unit cell is a regular water dodecahedron cell consisting of 20 water molecules with a methane molecule in the center. The geometries of water and methane are optimized at CCSD(T)/cc-pVTZ level. The BSSE-corrections are calculated for water-water and water-methane interaction energies as functions of the side length, l, of the dodecahedron cell at B3LYP/TZVP level in the range from 2.1 to 8.0A. The BSSE CP-corrected and dispersion-corrected potential energy surfaces (PES) of water-water and water-methane are useful for molecular dynamics simulation of gas clathrate-hydrates.     

Application of the independent molecule model to elucidate the dynamics of structure I methane hydrate: a second report

Two model systems of methane hydrate are constructed. One has a small cage surrounded by 12 large cages. The other has a large cage surrounded by four small cages and ten large cages. Three different H-bonding network patterns between waters are formed, and three random configurations of methane in each cage are chosen. A new method called the surface water fixed model is presented in which the energy minimum conformations for both model systems are preserved close to the X-ray crystallized structure. With normal mode analysis, we calculated frequencies of 2916.6 cm⁻¹ for a small cage at a centre, 2915.9 cm⁻¹ not at a centre, and 2911.7 cm⁻¹ for a large cage at a centre, and 2911.3 cm⁻¹ not at a centre. These frequencies are in moderate agreement with the corresponding Raman spectra, though not adequate. With our new method, however, it should be possible to improve agreement with the Raman spectra, if a model system vastly larger than the present model systems were constructed.     

空心光子晶体光纤在拉曼光谱仪中的应用

针对拉曼散射是一种弱散射,同时由于空心光子晶体光纤(HC—PCF)能显著增强光与填充介质之间的相互作用,提出将HC—PCF应用到拉曼光谱仪中,利用平面波展开法对HC—PCF的光子带隙与场分布进行模拟分析,探讨了HC—PCF的参数对拉曼散射强度的影响。通过理论研究发现光子晶体光纤可根据实际应用的需要,通过改变光纤的周期结构或包层气孔之间的间距来改变光子带隙,从而可传输不同波段的光。结果表明了HC—PCF在拉曼光谱仪中应用的可行性,为拉曼光谱仪在分子结构检测与分析提供了新的技术方法,也为HC—PCF的应用和研究开拓了广阔前景。     

天然气水合物物理化学性质和相平衡数据库系统的设计和开发

天然气水合物作为一种重要的潜在能源，一种导致全球气候变化的因素，一种地质灾害的诱发因素，已经引起了各领域科研工作者的广泛关注。因此，迫切需要建立一个天然气水合物信息系统，以便交流和共享各领域的研究成果。在本工作中，我们设计开发了关于天然气水合物基础性质的数据库系统。目前，本系统所收集的数据主要集中在与天然气水合物开采和应用技术相关的物理化学性质、晶体结构和相平衡数据。本系统不仅能够提供数据检索服务，还能够提供相平衡数据的网络计算功能。本文将对数据收集和数据库开发这两个方面进行讨论。     

A molecular dynamic study on the dissociation mechanism of SI methane hydrate in inorganic salt aqueous solutions

Gas hydrate is not only a potential energy resource, but also almost the biggest challenge in oil/gas flow assurance. Inorganic salts such as NaCl, KCl and CaCl₂ are widely used as the thermodynamic inhibitor to reduce the risk caused by hydrate formation. However, the inhibition mechanism is still unclear. Therefore, molecular dynamic (MD) simulation was performed to study the dissociation of structure I (SI) methane hydrate in existence of inorganic salt aqueous solution on a micro-scale. The simulation results showed that, the dissociation became stagnant due to the presence of liquid film formed by the decomposed water molecules, and more inorganic ions could shorten the stagnation-time. The diffusion coefficients of ions and water molecules were the largest in KCl system. The structures of ion/H₂O and H₂O/H₂O were the most compact in hydrate/NaCl system. The ionic ability to decompose hydrate cells followed the sequence of: Ca²⁺ > 2K⁺ > 2Cl⁻ > 2Na⁺.     

Application of the independent molecule model to elucidate the dynamics of structure I methane hydrate

Raman spectroscopy has exhibited the C–H stretch (A₁ mode) frequency ν₁ of hydrated methanes at 2915 cm⁻¹ for the 5¹² cage and 2905 cm⁻¹ for the 5¹²6² cage. These values are lower than the frequency of 2916.5 cm⁻¹ in gaseous methane. In this paper, we theoretically examine the Raman spectra observed in methane hydrate by normal mode analysis using the independent molecule model. By a breakdown of the symmetry, the four frequencies in modes A₁, E, T₂ and T₂ observed in gaseous methane are separated into nine frequencies in the hydrate. It is necessary to consider the anharmonic potential energy within methane and hydrogen bonding between methane hydrogen and water oxygen in order to get a result in qualitative agreement with experiment. The frequency in the 5¹²6² cage is shifted downward in comparison to the one in 5¹², and the frequencies in the both cages are also shifted downward compared with the frequencies in gas. Calculations are also reported for the isotopic methane (CD₄, ¹³CH₄) hydrates.     

The effects of wall roughness on the methane flow in nano-channels using non-equilibrium multiscale molecular dynamics simulation

This paper presents a non-equilibrium multiscale molecular dynamics simulation method to investigate the effects of periodic wall surface roughness on the structure and mass transfer of methane fluid through the silicon nano-channels. In order to accurately capture the trajectories and microstructure of methane nano-fluidics, the present modification of OPLS fully atomic model is employed. Meanwhile, we introduce the corresponding coarse-grained model to solve the problem of wall–fluid interaction for methane Poiseuille flow within silicon atomic walls using the classical Lorentz–Berthelot mixing rules. The geometries of the upper wall roughness are modeled by rectangular waves with different amplitudes and wavelengths. The three-dimensional number densities of C (H) atom and kinetic energy distribution plots give a clear observation of the impacts of surface roughness on the localization micro-information of methane fluid. Moreover, the slip length of fluid over rough surface decreases with the increase in amplitude. The diffusion coefficients appear anisotropic, and the radial distribution functions decrease with the increase in the amplitude. These properties should be taken into account in the design of energy-saving emission reduction nano-fluidic devices. All numerical results also indicate that the presented method not only can well solve the issue of wall–fluid interactions, but also could accurately predict the micro-information and dynamic properties of methane Poiseuille flow.     

化合物(C10H8N2)·2（H2O）的晶体结构及量子化学研究

以水热法制备了标题化合物(C10H8N2).2(H2O)单晶并用X射线单晶衍射仪测定了晶体结构,该晶体属于单斜晶系,C2空间群,晶胞参数为a=1.58589(16)nm,b=0.37770(4)nm,c=0.920210(11)nm,α=90.00°,β=114.0500(10)°,γ=90.00°,V=0.50335(7)nm3;最终偏差因子R1=0.0525,wR2=0.1311[对I>2θ(I)的衍射点]和R1=0.0661,wR2=0.1404[对所有衍射点]。化合物分子与水分子间由弱的O-H…N和O-H…O氢键作用形成了一维线形结构,该对称结构中两个吡啶环平面之间的夹角为40.7o。依据晶体结构数据使用G03程序对化合物进行了量子化学计算,探讨了化合物的分子优化结构、前线轨道、电荷分布、成键特征和稳定性。计算得到的分子键长、键角和X射线衍射的晶体结构数据基本符合,其差值证实晶体分子间氢键的存在。