Direct calculation of the hard-sphere crystal /Melt interfacial free energy

We present a direct calculation by molecular-dynamics computer simulation of the crystal/melt interfacial free energy gamma for a system of hard spheres of diameter sigma. The calculation is performed by thermodynamic integration along a reversible path defined by cleaving, using specially constructed movable hard-sphere walls, separate bulk crystal, and fluid systems, which are then merged to form an interface. We find the interfacial free energy to be slightly anisotropic with gamma = 0.62+/-0.01, 0.64+/-0.01, and 0. 58+/-0.01k(B)T/sigma(2) for the (100), (110), and (111) fcc crystal/fluid interfaces, respectively. These values are consistent with earlier density functional calculations and recent experiments.     

Method for computing the anisotropy of the solid-liquid interfacial free energy.

We present a method to compute accurately the weak anisotropy of the solid-liquid interfacial free energy, a parameter which influences dendritic evolution in materials with atomically rough interfaces. The method is based on monitoring interfacial fluctuations during molecular dynamics simulation and extracting the interfacial stiffness which is an order of magnitude more anisotropic than the interfacial free energy. We present results for pure Ni with interatomic potentials derived from the embedded atom method.     

利用扩展系综法计算水的自由能

利用扩展系综法得到了正则系综下水的TIP4P模型的自由能值为-21．485±0．035kJ/mol， 并与其他方法所得的结果作了比较.提出了选择该方法中关键参数(平衡因子)的有效方法， 并讨论了该方法的可移植性. 关键词： 自由能 TIP4P水模型 扩展系综 分子动力学模拟 水分子团     

Cu固液界面能的分子动力学计算

本文使用分子动力学方法对液相Cu中不同半径晶胚的生长和熔化行为进行了研究. 随着半径的增加, 晶胚生长的临界温度升高. 临界形核过冷度和晶胚半径倒数成正比关系, 这和经典形核理论一致. 由上述关系计算得到Cu的Gibbs-Thomson系数为1.12×10^-7 K·m, Cu的固液界面能为0.146 J/m², Cu的Turnbull系数为0.416, 这些计算值均与实验值一致. 关键词： 分子动力学 经典形核理论 固液界面能     

Experimental determination of solid-liquid interfacial energy for solid Sn in the Sn-Mg system

The equilibrated grain boundary groove shapes for solid Sn in equilibrium with the Sn-9 at.% Mg eutectic liquid were directly observed annealing a sample at the eutectic temperature for about 5 days with a radial heat flow apparatus. The thermal conductivities of the solid phase, κ_S, and the liquid phase, κ_L, for the groove shapes were measured. From the observed grain boundary groove shapes, the Gibbs-Thomson coefficient, the solid-liquid interfacial energy and grain boundary energy for solid Sn in equilibrium with the Sn-9 at.% Mg eutectic liquid have been determined to be (7.35 ± 0.36) × 10⁻⁸ Km, (136.41 ± 13.64) × 10⁻³ J m⁻² and (230.95 ± 25.40) × 10⁻³ J m⁻², respectively.     

Measurement of solid-liquid interfacial energy for solid Zn in the Zn-Cd eutectic system

The equilibrated grain boundary groove shapes for the Zn solid solution in Zn-Cd liquid solutions were directly observed. From the observed grain boundary groove shapes, the Gibbs-Thomson coefficient for solid Zn (Zn-15 wt.% Cd) in Zn-Cd liquid solutions has been determined to be (2.5 ± 0.1) × 10⁻⁸ Km by a direct method. The solid-liquid interfacial energy between solid Zn and Zn-Cd liquid solution has been obtained to be (165.5 ± 19.0) mJ/m² from the Gibbs-Thomson equation. The grain boundary energy for the same alloy has been determined as (317.8 ± 39.9) mJ/m². The thermal conductivities of the solid and liquid phases at the eutectic composition and temperature have also been measured.     

On the temperature dependence of solid-liquid interfacial free energies per unit area

The solid-liquid interfacial free energy per unit area of metals has been found to increase with decrease of temperature. Consequently the corresponding temperature coefficient is negative.     

Orientation dependence of the solid/liquid interfacial free energy in binary systems

A first-order theory of compositional segregation at solid/liquid interfaces, based on a pair-bonded, lattice-liquid interfacial model, has been applied to predict the effect of segregation on the orientation dependence of the interfacial free energy in binary metallic systems. The results show that the sharpness of the cusps in the gamma plot is reduced due to preferential segregation at layer edges as compared to layer faces, and cusps may be eliminated under certain conditions. The reduction in cusp sharpness is the greatest when the composition difference of the solid and liquid phases is large and the solutions are appreciably non-ideal. The relative reduction of sharpness due to segregation is less pronounced for cusps which are sharper in the unsegregated condition, so segregation tends to smooth the form of the gamma plot. Graphical results are presented for calculation of segregational anisotropy effects in general systems.     

Temperature Integration: An efficient procedure for calculation of free energy differences

We propose a method, Temperature Integration, which allows an efficient calculation of free energy differences between two systems of interest, with the same degrees of freedom, which may have rough energy landscapes. The method is based on calculating, for each single system, the difference between the values of lnZ$lnZ$ at two temperatures, using a Parallel Tempering procedure. If our two systems of interest have the same phase space volume, they have the same values of lnZ$lnZ$ at high-T$T$, and we can obtain the free energy difference between them, using the two single-system calculations described above. If the phase space volume of a system is known, our method can be used to calculate its absolute (versus relative) free energy as well. We apply our method and demonstrate its efficiency on a “toy model” of hard rods on a 1-dimensional ring.     

Direct calculation of intermolecular potential energy surfaces

A variation perturbation method is presented for the direct calculation of intermolecular interaction energies. The theory is based on valence bond ideas but avoids the full evaluation of the matrix elements by expansion in powers of interchange, a procedure which is valid for small overlap between the systems. The participating excited states are regarded as polarized pseudo-states and are determined by optimizing the long-range multipole-multipole part of the interaction energy. The validity of these ideas is illustrated by a calculation of the He-He interaction. A remarkable simplification is pointed out, in which the interaction energy is given almost exactly by the sum of the repulsive term, calculated as zero + single interchange, plus the long-range interaction.     

KDP晶体固-液界面吸附行为的分子模拟研究

通过构建晶体表面-KDP分子界面吸附结构模型, 采用分子动力学和密度泛函计算方法研究KDP分子在(001)和(010)面吸附的物理化学过程, 考察了温度对物理吸附行为的影响. 研究表明: KDP晶体表面的吸附过程和生长习性主要由化学吸附主导, 化学吸附能的计算表明[K-O₈]基元在(001)界面的结合能是(010)界面结合能的2.86倍; 在饱和温度附近, [H₂PO₄]^-阴离子在KDP界面的物理结合能随温度的变化呈现振荡特征, 溶液中有较多的离子团簇形成, 溶液变得很不稳定; 当温度从323 K降低至308 K时, 水分子在界面的结合能总体呈下降趋势, 而KDP分子在界面的吸附能总体呈上升趋势, 脱水过程是水分子和[H₂PO₄]^-阴离子在固液界面边界层竞争吸附的结果. 研究结果对确足晶体生长界面动力学过程发展和完善晶体生长理论有重要意义. 关键词： 分子动力学 双层结构模型 结合能     

Identification of potential inhibitors of coronavirus hemagglutinin-esterase using molecular docking,molecular dynamics simulation and binding free energy calculation

Molecular Diversity - The pandemic outbreak of the Corona viral infection has become a critical global health issue. Biophysical and structural evidence shows that spike protein possesses a high...     

Faddeev-Born-Oppenheimer equations for molecular three-body systems: Adiabatic calculation of 9Be

The low-lying states of ⁹Be are calculated in the α-particle cluster model. The calculation is performed using a rotationally invariant molecular formulation of the three-body problem based on the Faddeev equations, which are solved for the α + n + α system in the adiabatic limit with the α-α interaction turned off. The resulting two-centre wave function is used to formulate an ansatz for the solution of the full hamiltonian of the system where all three particles interact. Unlike the traditional molecular approach, the ansatz we propose allows for the coupling between the movement of the light particle and the rotational motion of the heavy particles. This leads to a set of coupled ordinary differential equations for the three-body wave function that has good total angular momentum and parity. Although only one Born-Oppenheimer molecular energy curve is considered, all adiabatic corrections due to Coriolis coupling effects, mass polarization and derivatives of the two-centre wave function with respect to the separation distance between the α-particles are taken into account. Comparison with exact Faddeev results is presented for the ground-state energies of ⁹Be in a model problem where the α-α interaction is turned off. The validity of the molecular approach for small mass ratios between the heavy particle and the light particle is studied in a very general framework.     

Direct calculation of bubble points for alkane mixtures by molecular simulation

This paper extends to flexible molecules an algorithm proposed earlier for the calculation of bubble points of simple fluids by Monte Carlo simulation (Ungerer, P., Boutin, A., and Fuchs, A. H., 1999, Molec. Phys., 97, 523). This algorithm is based on a pseudo-ensemble in which global volume, temperature and liquid phase mole numbers are fixed. A configurational bias method is used to treat flexible molecules, and the underlying assumptions regarding the molecular partition function for flexible chains are discussed. Molecular interactions are determined with an anisotropic united atoms intermolecular potential, recently optimized to represent vapour-liquid phase equilibria of n-alkanes. Two applications examples are given, concerning a binary mixture (methane + n-pentane) and a ternary system (methane + propane + n-decane) for which experimental data are available. Satisfactory convergence is obtained, except in the vicinity of critical conditions. Densities and vapour phase compositions are well represented. Bubble pressures appear significantly underestimated, however. The origin of this discrepancy and remedial methods are discussed.     

Reflection anisotropy spectroscopy: A new probe for the solid-liquid interface

Introducing reflection anisotropy spectroscopy (RAS) as a new probe for solid-liquid interfaces, we present results for the Au(110)/electrolyte interface which serves as a model system. We demonstrate that RAS is sensitive to surface phase transitions, step morphology, and electronic surface states. Using an empirical approach, the RA spectra are reproduced and features are identified which reflect the known character of the bias voltage driven (2x1) to (1x1) phase transition. RAS is established as an experimental technique to probe the electronic structure of solid-liquid interfaces in real time to study a wide range of interface properties.     

Simple inequality for the free energy of disordered systems

It is proved that the free energy of a disordered system described by a quadratic form in Bose or Fermi operators with random coefficients, calculated in the simplest approximation for the associated eigenvalue problem, gives the upper (Bose case) and lower (Fermi case) bounds for the exact free energy.