狭小间距间Cu/Al薄膜相互作用的分子动力学模拟

采用分子动力学模拟软件基于Lennard-Jones-9-6势函数研究了狭小间距Cu/Al纳米薄膜间的相互作用. 我们通过计算薄膜表面单位面积上的范德华相互作用能σ_E,综合性地讨论了非接触Cu/Al薄膜间的相互作用.结果显示,当两薄膜的间距从12Å减小到3Å时,相互作用能呈现两个阶段：起初几乎不变,然后迅速增大.临界间距在7 Å附近.在两薄膜相互靠近的过程中,相互作用能受体系尺寸、空位缺陷尺寸、表面涂层及薄膜间距的影响较大,然而几乎不受空位缺陷形状的影响.     

低能Cu原子簇沉积薄膜的分子动力学模拟

用分子动力学计算机模拟研究了能量为5—20eV/atorn,结构为正二十面体的(Cu)₁₃原子簇在Cu（001）表面的沉积过程.采用紧束缚势同Moliers势的结合描述Cu原子间相互作用通过原子簇-衬底相互作用的“快照”研究沉积的动态过程．结果表明,当入射能量较低时,轰击弛豫后,入射原子簇在衬底表面发生重构,生成很好的外延层,靶没有任何损伤．随着轰击能量的增加,原子簇原子穿入靶的深度增加.当入射能量达到20eV/atom时,原子簇完全穿入靶并开始造成辐照损伤,表面出现空位,靶内产生间     

Au纳米薄膜的熔化机理及其结构演变的分子动力学模拟

利用分子动力学模拟详细研究了不同厚度的Au纳米薄膜的熔化机理和结构演变. 模拟结果表明所有Au纳米薄膜的熔化行为分为两个阶段,即表面预熔和均相熔化. 只有最外层原子出现了预熔化行为, 其他内层原子在均相熔化之前始终保持稳定的固态,这与零维的Au纳米团簇和一维的Au纳米线的预熔化行为是不同的. 同时Au纳米薄膜的熔化温度随着薄膜厚度的增加而升高. 在预熔化过程中,在原子水平上发现了所有的Au纳米薄膜的f100g晶面向f111g晶面转变的表面重建过程. 对于最薄的L2纳米薄膜,当温度低于500 K 时表面应力不能诱导这样的表面重建. 然而一维的Au纳米线在更低温度下就能够观察到了由表面应力诱导的表面重建过程. 这主要是因为Au纳米线具有更高的比表面积所导致的. 另外研究结果还表明当模拟温度达到某一特定值时,由双原子层组成的Au纳米薄膜能够分裂成一维的纳米线.     

Mo纳米薄膜热力学性质的分子动力学模拟

采用改进嵌入原子法(MAEAM),通过经典的分子动力学(MD)模拟计算了高熔点过渡金属体心立方(bcc) Mo块体Gibbs自由能和表面能. 对于纳米薄膜的热力学数据,比如Gibbs自由能等,可以看成是薄膜内部原子和表面原子两部分数据之和,然后根据薄膜的体表原子之比就可以直接计算出总的自由能,并由此可以得到热力学性质与薄膜尺寸及温度的定量关系式. 分别计算了bcc Mo块体及其纳米尺寸薄膜的自由能和热容,结果表明,Mo纳米薄膜的热力学性质具有尺寸效应,并且在薄膜尺寸小于15—20nm时,这种效应变得非常明 关键词： 改进嵌入原子法 Mo纳米薄膜 表面自由能 热容     

金刚石表面无定形碳氢薄膜生长的分子动力学模拟

利用分子动力学模拟方法研究了CH₂基团轰击金刚石(111)面所形成的无定形碳氢薄膜(a-C:H)的生长过程. 结构分析表明, 得到的无定形碳氢薄膜中碳原子的局域结构(如C–C第一近邻数)与其中氢原子的含量密切相关. CH₂ 基团入射能量的增加会导致得到的薄膜的氢含量降低, 从而改变薄膜中类sp³成键碳原子的比例.     

分子动力学模拟铜薄膜的热导率

采用分子动力学(MD)方法模拟铜薄膜的热导率,给出了厚度在100~400nm、温度在100~600K范围内铜薄膜热导率对尺寸及温度的依赖关系.     

氩晶体薄膜法向热导率的分子动力学模拟

结合卫星“微型核”的特点，研究电介质薄膜中的导热机理以及薄膜厚度对导热系数的影响.以结构较为简单、具有可靠势能函数，实验数据较为丰富和可靠的氩的(fcc)晶体为模型,采用平衡分子动力学方法(EMD)和各向异性非平衡分子动力学方法(NEMD)计算了氩晶体及其法向薄膜的热导率,并与实验结果进行比较.模拟结果表明，氩晶体纳米薄膜的热导率显著小于对应大体积晶体的实验值，具有明显的尺寸效应.在氩薄膜厚度为2.124—5.310nm的模拟范围内,薄膜的法向热导率随着薄膜厚度的增加而呈近似线性增加. 关键词： 热导率 纳米薄膜 尺寸效应 平衡分子动力学 非平衡分子动力学     

类金刚石薄膜力学特性的分子动力学模拟

基于Brenner的REBO势函数,利用分子动力学方法模拟了含氢量不同的类金刚石薄膜的纳米压痕过程,依据得到的加载卸载曲线,计算了薄膜的刚度、硬度以及弹性模量.结果表明:类金刚石薄膜的硬度由氢含量和sp³键含量两个因素共同决定;当薄膜中氢含量小于39% 时,薄膜硬度主要取决于sp³键含量,sp³键越多,硬度越高;当薄膜中氢含量达到52%,薄膜硬度则显著下降,此时氢的作用占据主导地位. 关键词： 类金刚石薄膜 分子动力学模拟 纳米压痕 硬度     

分子动力学模拟H原子与Si的表面相互作用

通过分子动力学模拟了入射能量对H原子与晶Si表面相互作用的影响. 通过模拟数据与实验数据的比较, 得到H原子吸附率随入射量的增加 呈先增加后趋于平衡的趋势. 沉积的H原子在Si表面形成一层氢化非晶硅薄膜, 刻蚀产物(H₂, SiH₂, SiH₃和SiH₄)对H原子吸附率趋于平衡有重要影响, 并且也决定了样品的表面粗糙度. 当入射能量为1 eV时, 样品表面粗糙度最小. 随着入射能量的增加, 氢化非晶硅薄膜中各成分(SiH, SiH₂, SiH₃)的量以及分布均有所变化. 关键词： 分子动力学 吸附率 表面粗糙度 氢化非晶硅薄膜     

Al(001)表面上沉积Ti薄膜的分子动力学模拟

采用分子动力学模拟方法,研究了Ti原子连续沉积于Al(001)表面上的薄膜生长过程,分析了入射能量为0.1、5 eV和衬底温度为300、700 K时的界面结合及微观结构.模拟结果表明,增加入射能量和衬底温度,使Ti薄膜的表面越光滑;通过径向分布函数和键对分析技术对薄膜微观结构进行分析,发现衬底温度时薄膜微观结构影响较大,温度300 K及以下时,Ti薄膜主要是FCC结构,随着温度升高,FCC结构成分减少,无序结构成分增加,而入射能量则对薄膜微观结构没有明显影响.     

基态原子与理想金属Au表面间的范德瓦尔斯作用

研究了基态碱金属原子与理想金属Au表面间的范德瓦尔斯(vdW)作用.通过分析电四极跃迁对vdW的贡献,构建了计算超精细能级碱金属原子与理想金属表面间vdW作用系数C3的理论模型.以85Rb、133Cs为例,计算了其基态原子超精细能级的C3系数.其中85Rb: 52S1/2 (F=2)及52S1/2 (F=3)对应的C3系数分别为:2.2409 及2.2425 ;133Cs: 62S1/2 (F=3)及62S1/2 (F=4)分别对应 2.4480 及2.4538 .研究还发现随着 的增大,C3增大,z (原子与金属表面之间的距离)不变时,原子与理想金属表面间vdW作用增强. 这一研究在实现原子囚禁及介质表面量子反射等方面具有重要意义     

基态原子与理想金属Au表面间的范德瓦尔斯作用

研究了基态碱金属原子与理想金属Au表面间的范德瓦尔斯(vdW)作用.通过分析电四极跃迁对vdW的贡献,构建了计算超精细能级碱金属原子与理想金属表面间vdW作用系数C3的理论模型.以85Rb、133Cs为例,计算了其基态原子超精细能级的C3系数.其中85Rb: 52S1/2 (F=2)及52S1/2 (F=3)对应的C3系数分别为:2.2409 及2.2425 ;133Cs: 62S1/2 (F=3)及62S1/2 (F=4)分别对应 2.4480 及2.4538 .研究还发现随着 的增大,C3增大,z (原子与金属表面之间的距离)不变时,原子与理想金属表面间vdW作用增强. 这一研究在实现原子囚禁及介质表面量子反射等方面具有重要意义     

The electrostatic contribution to the long-range interactions between tungsten and oxide surfaces under ultrahigh vacuum

The force gradient between a tungsten tip and a flat oxide substrate has been measured as a function of tip-to-surface distance, D, using an oscillating cantilever technique under Ultrahigh Vacuum. We analyze the relative contribution of van der Waals and electrostatic forces between a W tip and SiO₂, TiO₂ and MgO substrates. The observed Hamaker constants are in agreement with the Lifshitz theory, while we tentatively correlate the surface charge densities with the gap of the oxides.     

基于最新势能面的C(1D)+H2反应的环聚合分子动力学研究

本文利用环聚合分子动力学方法对C(¹D)+H₂反应开展了详细的理论研究. 计算中使用了最近构建的Zhang-Ma-Bian(ZMB)从头算势能面,该势能面对锥形交叉附近区域以及范德华区域均有精确的描述. 环聚合分子动力学计算得到的热反应速率常数与最新实验值吻合很好. 与前人计算结果比较,发现在?¹A′电子基态的ZMB-a势能面上获得的反应速率常数远大于前人构建的RKHS势能面上的结果,这是由于ZMB势能面上的范德华鞍具有与之前势能面上的范德华阱完全不同的动态学作用,表明环聚合分子动力学方法能够处理范德华作用引起的势能面拓扑结构所导致的动态学效应. 本文还揭示了b¹A′′电子激发态ZMB-b势能面以及量子效应对反应的重要性.     

高次激发相关能在构建HCN-He亚光谱精度势能面中的角色:通过实验高分辨率光谱进行严格检测

Interpreting high-resolution rovibrational spectra of weakly bound complexes commonly requires spectroscopic accuracy (<1 cm^-1) potential energy surfaces (PES). Constructing high-accuracy ab initio PES relies on the high-level electronic structure approaches and the accurate physical models to represent the potentials. The coupled cluster approaches including single and double excitations with a perturbational estimate of triple excitations (CCSD(T)) have been termed the "gold standard" of electronic structure theory, and widely used in generating intermolecular interaction energies for most van der Waals complexes. However, for HCN-He complex, the observed millimeter-wave spectroscopy with high-excited resonance states has not been assigned and interpreted even on the ab initio PES computed at CCSD(T) level of theory with the complete basis set (CBS) limit. In this work, an effective three-dimensional ab initio PES for HCN-He, which explicitly incorporates dependence on the Q₁ (C-H) normal-mode coordinate of the HCN monomer has been calculated at the CCSD(T)/CBS level. The post-CCSD(T) interaction energy has been examined and included in our PES. Analytic two-dimensional PESs are obtained by least-squares fitting vibrationally averaged interaction energies for v₁(C-H)=0, and 1 to the Morse/Long-Range potential function form with root-mean-square deviations (RMSD) smaller than 0.011 cm^-1. The role and significance of the post-CCSD(T) interaction energy contribution are clearly illustrated by comparison with the predicted rovibrational energy levels. With or without post-CCSD(T) corrections, the value of dissociation limit (D₀) is 8.919 or 9.403 cm^-1, respectively. The predicted millimeter-wave transitions and intensities from the PES with post-CCSD(T) excitation corrections are in good agreement with the available experimental data with RMS discrepancy of 0.072 cm^-1. Moreover, the infrared spectrum for HCN-He complex is predicted for the first time. These results will serve as a good starting point and provide reliable guidance for future infrared studies of HCN doped in (He)_n clusters.     

The Casimir Problem of Spherical Dielectrics: A Solution in Terms of Quantum Statistical Mechanics

The Casimir energy for a compact dielectric sphere is considered in a novel way, using the quantum statistical method introduced by Høye and Stell and others. Dilute media are assumed. It turns out that this method is a very powerful one: we are actually able to derive an expression for the Casimir energy that contains also the negative part resulting from the attractive van der Waals forces between the molecules. It is precisely this part of the Casimir energy that has turned out to be so difficult to extract from the formalism when using the conventional field-theoretic methods for a continuous medium. Assuming a frequency cutoff, our results are in agreement with those recently obtained by G. Barton.     

p53-MDM2相互作用的分子力学和动力学研究

p53-MDM2相互作用的抑制已经成为治疗癌症的新方法. 本文将分子动力学模拟和MM-PBSA(molecular mechanics/passion-Boltzman surface area)方法结合起来研究MDM2-p53相互作用机制. 结果证明范德华相互作用驱动了MDM2与p53的结合. 基于残基-残基相互作用的计算不仅证明p53的三个残基Phe19′, Trp23′和Leu26′与MDM2有较强的相互作用,而且还发现另外两个残基Leu22′和Pro27′也与MDM2有较强的相互作用,这为抗癌药物的设计提供了新靶标. 同时也证明CH-CH,CH-π和π-π相互作用驱动了p53在MDM2疏水性裂缝中的结合.     

Solvent effects on the intrinsic enhancement factors of the triplet exciplex generated by photoinduced electron transfer reaction between eosin Y and duroquinone

The spin dynamics of the duroquinone anion radical (DQ^?-) generated by photoinduced electron transfer reactions from triplet eosin Y (³EY^2-) to DQ have been studied by using transient absorption and pulsed EPR spectroscopy. Unusual net-absorptive electron spin polarization plus net-emissive polarization were observed, suggesting the production of the triplet exciplex or contact radical pair as the reaction intermediate. The kinetic parameters and intrinsic enhancement factors of the electron spin polarization were determined in various alcoholic solvents. The net-absorptive electron spin polarization was also observed in ethanol-water mixed solvents. The solvent effects on the radical yield are analysed on the basis of a stochastic Liouville equation established for the magnetic field effects on the radical yield. The zero-field splitting constants of the triplet exciplex are estimated from the solvent viscosity dependence of the enhancement factors due to spin-orbit coupling induced depopulation of the reaction intermediate.     

The Effect of Nanoscale Roughness on Long Range Interaction Forces

A model was developed to calculate the long range van der Waals and electrostatic energies between a rough colloidal particle and a smooth solid plate in aqueous solutions. The particle roughness was modeled as hemispherical asperities distributed uniformly over the surface. Because of the assumption of additive potentials used in calculating the electrostatic force, the model is most accurate when the particle/plate separation is larger than several Debye screening lengths, such as near the location of the secondary minimum. The model predicts that such roughness reduces the depth of the secondary minimum and pushes it to larger separation distances. The model also predicts that the height of the primary energy barrier, which controls the dispersion stability, is substantially lowered by the asperities.Experimental validation of the model was achieved by measuring the potential energy profile between individual, 15µm diameter polystyrene latex spheres and a smooth glass plate around the location of the secondary energy minimum using the optical technique of total internal reflection microscopy (TIRM). When compared to predictions made assuming perfectly smooth surfaces, the measured well depths are consistently found to be lower than expected. Excellent agreement can be achieved, however, by adding asperities with a height of order 25nm to the particle surface. These measurements are some of the first direct measurements of the effect of roughness on interaction energies.