碳纳米管阵列水渗透性质的研究

碳纳米管阵列组成的碳纳米管分子膜在生物学分子器件等方面有重要应用. 本文利用分子动力学方法计算研究水分子对(11, 11)碳纳米管阵列的渗透过程. 结果发现, 只有当阵列间隙面积大于57.91 Ų时, 水分子才能进入阵列间隙中, 并揭示了碳管内部、阵列间隙内水分子结构随相邻碳管间距变化的演化趋势以及管内外水分子电偶极矩的分布特性.     

形变碳纳米管中水的输运行为研究

水分子通过碳纳米管的运输行为对认识生命的新陈代谢活动、海水淡化和纳米运输器件有着重要的参考作用.本文通过分子动力学的方法研究了水分子通过形变碳纳米管的运输行为,即椭圆柱状碳纳米管的离心率e对管内水分子输运的影响.结果发现椭圆柱状碳纳米管的离心率对管内水分子的偶极矩概率分布、径向函数分布和流量有重要的影响作用.分析认为碳纳米管的形变使管内水分子的偶极矩态及其运输状态发生变化;同时也发现在一定范围内通过改变碳纳米管的形状能起到分子开关的作用.     

形变碳纳米管中水的输运行为研究

水分子通过碳纳米管的运输行为对认识生命的新陈代谢活动、海水淡化和纳米运输器件有着重要的参考作用. 本文通过分子动力学的方法研究了水分子通过形变碳纳米管的运输行为, 即椭圆柱状碳纳米管的离心率e对管内水分子输运的影响. 结果发现椭圆柱状碳纳米管的离心率对管内水分子的偶极矩概率分布、径向函数分布和流量有重要的影响作用. 分析认为碳纳米管的形变使管内水分子的偶极矩态及其运输状态发生变化; 同时也发现在一定范围内通过改变碳纳米管的形状能起到分子开关的作用.     

Asymmetry of the water flux induced by the deformation of a nanotube

The behavior of nano-confined water is expected to be fundamentally different from the behavior of bulk water.At the nanoscale,it is still unclear whether water flows more easily along the convergent direction or the divergent one,and whether a hourglass shape is more convenient than a funnel shape for water molecules to pass through a nanotube.Here,we present an approach to explore these questions by changing the deformation position of a carbon nanotube.The results of our molecular dynamics simulation indicate that the water flux through the nanotube changes significantly when the deformation position moves away from the middle region of the tube.Different from the macroscopic level,we find water flux asymmetry(water flows more easily along the convergent direction than along the divergent one),which plays a key role in a nano water pump driven by a ratchet-like mechanism.We explore the mechanism and calculate the water flux by means of the Fokker-Planck equation and find that our theoretical results are well consistent with the simulation results.Furthermore,the simulation results demonstrate that the effect of deformation location on the water flux will be reduced when the diameter of the nanochannel increases.These findings are helpful for devising water transporters or filters based on carbon nanotubes and understanding the molecular mechanism of biological channels.     

The structure and dynamics of water inside armchair carbon nanotube

In this paper we present some simulation results about the behaviour of water molecules inside a single wall carbon nanotube (SWNT). We find that the confinement of water in an SWNT can induce a wave-like pattern distribution along the channel axis, similar phenomena are also observed in biological water channels. Carbon nanotubes(CNTs) can serve as simple nonpolar water channels. Molecular transport through narrow CNTs is highly collective because of tight hydrogen bonds in the protective environment of the pore. The hydrogen bond net is important for proton and other signal transports. The average dipoles of water molecules inside CNTs (7,7), (8,8) and (9,9) are discussed in detail. Simulation results indicate that the states of dipole are affected by the diameter of SWNT. The number of hydrogen bonds, the water--water interaction and water--CNT interaction are also studied in this paper.     

The effect of the target structure and composition on the ejection and transport of polymer molecules and carbon nanotubes in matrix-assisted pulsed laser evaporation

Matrix-assisted pulsed laser evaporation (MAPLE) is a prominent member of a broad and expanding class of laser-driven deposition techniques where a matrix of volatile molecules absorbs laser irradiation and provides the driving force for the ejection and transport of the material to be deposited. The mechanisms of MAPLE are investigated in coarse-grained molecular dynamic simulations focused on establishing the physical regimes and limits of the molecular transfer from targets with different structures and compositions. The systems considered in the simulations include dilute solutions of polymer molecules and individual carbon nanotubes (CNTs), as well as continuous networks of carbon nanotubes impregnated with solvent. The polymer molecules and nanotubes are found to be ejected only in the ablation regime and are incorporated into matrix-polymer droplets generated in the process of the explosive disintegration of the overheated matrix. The ejection and deposition of droplets explain the experimental observations of complex surface morphologies in films deposited by MAPLE. In simulations performed for MAPLE targets loaded with CNTs, the ejection of individual nanotubes, CNT bundles, and tangles with sizes comparable or even exceeding the laser penetration depth is observed. The ejected CNTs align along the flow direction in the matrix plume and tend to agglomerate into bundles at the initial stage of the ablation plume expansion. In a large-scale simulation performed for a target containing a network of interconnected CNT bundles, a large tangle of CNT bundles with the total mass of 50 MDa is separated from the continuous network and entrained with the matrix plume. No significant splitting and thinning of CNT bundles in the ejection process is observed in the simulations, suggesting that fragile structural elements or molecular agglomerates with complex secondary structures may be transferred and deposited to the substrate with the MAPLE technique.     

Single-Walled Carbon Nanotubes Acting as Controllable Transport Channels

The motion and equilibrium distribution of water molecules adsorbed inside neutral and negatively charged singlewalled carbon nanotubes (SWNTs) have been studied using molecular dynamics simulations (MDSs) at room temperature based on CHARMM (Chemistry at HARvard Molecular Mechanics) potential parameters. We find that water molecules have a conspicuous electropism phenomenon and regular tubule patterns inside and outside the charged tube wall. The analyses of the motion behaviour of water molecules in the radial and axial directions show that by charging the SWNT, the adsorption efficiency is greatly enhanced, and the electric field produced by the charged SWNTs prevents water molecules from flowing out of the nanotube. However, water molecules can travel through the neutral SWNT in a fluctuating manner. This indicates that by electrically charging and uncharging the SWNTs, one can control the adsorption and transport behaviour of polar molecules in SWNTs for using as a stable storage medium or long transport channels. The transport velocity can be tailored by changing the charge on the SWNTs, which may have a further application as modulatable transport channels.     

Electrical switching in metallic carbon nanotubes

We present first-principles calculations of quantum transport which show that the resistance of metallic carbon nanotubes can be changed dramatically with homogeneous transverse electric fields if the nanotubes have impurities or defects. The change of the resistance is predicted to range over more than 2 orders of magnitude with experimentally attainable electric fields. This novel property has its origin that backscattering of conduction electrons by impurities or defects in the nanotubes is strongly dependent on the strength and/or direction of the applied electric fields. We expect this property to open a path to new device applications of metallic carbon nanotubes.     

Thermal conductivity and thermal rectification in carbon nanotubes with geometric variations of doped nitrogen: Non-equilibrium molecular dynamics simulations

The thermal conductivity of carbon nanotubes with geometric variations of doped nitrogen is investigated. The phenomenon of thermal rectification shows that the heat transport is preferably in one direction. The asymmetric heat transport of the triangular single-nitrogen-doped carbon nanotubes (SNDCNTs) is larger than that of the parallel various-nitrogen-doped carbon nanotubes (VNDCNTs).     

单壁碳纳米管受限空间内水的分布

碳纳米管管腔作为分子物质的纳米通道,其储存或输送水的能力具有重要研究价值.为了研究碳纳米管管腔受限空间对水分子团簇结构和分布的影响,本文采用分子动力学方法探究了管径、手性和温度对单壁碳纳米管管腔内水的结构和分布的影响.结果表明:在常温下,管径尺寸范围为1.018—1.253 nm的单壁碳纳米管管内易形成有序的多元环水结构,此范围以外碳纳米管管内难以形成水的有序结构;且随着管径尺寸增大,多元环水呈现由三元环至六元环的结构变化;范德瓦耳斯势分布分析表明,在上述管径范围内,水分子趋向于贴近碳纳米管管壁分布而形成水的有序结构.对比管径尺寸差别较小的碳纳米管,其手性对多元环水结构影响不大.多元环水结构的稳定性表现出温度依赖性,管径较大的碳纳米管内的多元环水的有序结构更易随温度升高而消失.     

Transport of liquid mercury under pressure in double-walled carbon nanotubes

In this paper, transport of liquid mercury under pressure through double-walled carbon nanotubes is studied using classical molecular dynamics simulations in conjunction with a pressure control model. The results indicate that wetting of double-walled carbon nanotubes by mercury occurs above a threshold pressure of liquid mercury. Liquid mercury can be transported through the inner tube of double-walled carbon nanotubes with the continuous increase of its pressure. The threshold pressure of liquid mercury decreases and the transport efficiency increases greatly with enlarging the inner tube size. The space between the two walls of double-walled carbon nanotubes can also transport the liquid mercury while the distance between the two walls is much larger than the radius of the inner tube. Transport efficiency of double-walled carbon nanotubes is a little lower than that of single-walled carbon nanotubes while double-walled carbon nanotubes transport liquid more steadily than single-walled carbon nanotubes.     

Effect of molecular structure on fluid transport through carbon nanotubes

We perform molecular dynamics simulations to study the transport of geometrically modified water models through channels of carbon nanotube (CNT) membranes. We use two modifications to an existing water model (extended simple point charge SPC/E) as representative surrogates of molecular fluids: (1) bent model (model B) in which the HOH angle is varied while keeping the dipole moment constant by adjusting the OH bond length and (2) modified bent model (model MB) in which the HOH angle changes without any change in OH bond length thereby changing the dipole moment. Interestingly, we find that the fluid transport is a nonmonotonic function of the bond angle for both fluid models. This observed trend is not anticipated based on the fluid density as a function of the bond angle inside and outside of the nanotube channel. However, the average residence time of transmitted molecules through the channel provides an approximately inverse linear correlation with the observed flux, independent of the fluid model. Based on these correlations, we have developed an empirical design parameter connecting fluid transport through CNTs as a function of average occupancy (number of fluid molecules inside the nanotube) and the average residence time. Our results suggest that transport through carbon nanotubes can be sensitive to small changes in the structure of fluid molecules that can potentially be utilised for mixture separation.     

水分子链受限于单壁碳纳米管结构的密度泛函理论研究

本文采用第一性原理的密度泛函理论,主要以(6,6)Armchair型,(11,0)Zigzag型单壁碳纳米管为研究对象,研究了水分子链在碳纳米管内部吸附的稳定结构,以及结合能随其结构的变化.结果表明:当水分子链受限于碳纳米管内部时,引起碳纳米管直径收缩,这主要是由于水分子链与碳纳米管之间的氢键作用以及范德华弱相互作用所引起的.随着碳纳米管半径的增加,两种单体之间的结合能逐渐减小,但当碳纳米管半径增加至6.78时,其结合能又有所增加,这是由于在优化过程中,水分子链单体之间的氢键作用大于水分子链与碳纳米管之 关键词： 水分子链/单壁碳纳米管 密度泛函理论 结构稳定性     

石墨烯纳米带卷曲效应对其电子特性的影响

石墨烯纳米带 (GNRs) 是一种重要的纳米材料, 碳纳米管可看作是GNRs卷曲而成的无缝圆筒. 利用基于密度泛函理论的第一性原理方法, 系统研究了GNRs卷曲变形到不同几何构型时, 其电子特性, 包括能带结构 (特别是带隙) 、态密度、透射谱的变化规律. 结果表明: 无论是锯齿型GNRs (ZGNRs) 或扶手椅型GNRs (AGNRs), 在其卷曲成管之前, 其电子特性对卷曲形变均不敏感, 这意味着GNRs的电子结构及输运特性有较强地抵抗卷曲变形的能力. 当GNRs 卷曲成管后, ZGNRs和AGNRs表现出完全不同的性质, ZGNRs几乎保持金属性不变或变为准金属; 但AGNRs的电子特性有较大的变化, 出现不同带隙半导体、准金属之间的转变, 这也许密切关系到碳纳米管管口周长方向上的周期性边界条件及量子禁锢的改变. 这些研究对于了解GNRs电子特性的卷曲效应、以及GNRs与碳纳米管电子特性的关系 (结构与特性的关系) 有重要意义. 关键词： 石墨烯纳米带 卷曲效应 电子特性 密度泛函理论     

Proton transport through water-filled carbon nanotubes

Proton transfer along 1D chains of water molecules inside carbon nanotubes is studied by simulations. Ab initio molecular dynamics and an empirical valence bond model yield similar structures and time scales. The proton mobility along 1D water chains exceeds that in bulk water by a factor of 40, but is reduced if orientational defects are present. Excess protons interact with hydrogen-bonding defects through long-range electrostatics, resulting in coupled motion of protons and defects.     

液体水银在碳纳米管中传输的压力控制模型

碳纳米管在纳米技术中有一个很重要的应用,就是它可以作为纳米管道传输液体. 本文用分子动力学模拟方法,结合一个液体压力控制模型,对液体水银由于外部压力作用在碳纳米管中传输的现象进行研究. 研究结果表明,当液体水银的内部压强超过一个临界值时,液体水银能够浸入到碳纳米管内部;不断增大液体内部的压强,碳纳米管可以连续地传输液体;而当对液体水银进行循环加压时,碳纳米管可以间断地传输液体水银. 关键词： 碳纳米管 流体传输 分子动力学     

液体水银在碳纳米管中传输的压力控制模型

碳纳米管在纳米技术中有一个很重要的应用，就是它可以作为纳米管道传输液体. 本文用分子动力学模拟方法，结合一个液体压力控制模型，对液体水银由于外部压力作用在碳纳米管中传输的现象进行研究. 研究结果表明，当液体水银的内部压强超过一个临界值时，液体水银能够浸入到碳纳米管内部；不断增大液体内部的压强，碳纳米管可以连续地传输液体；而当对液体水银进行循环加压时，碳纳米管可以间断地传输液体水银.     

基于碳纳米管分子封装的一维电子波函数扫描

利用第一性原理,设计并研究了一类基于单臂碳纳米管的分子封装的分子体系．计算表明,半环葫芦脲类化合物可有效封装碳纳米管,引入微弱的分子间相互作用,对碳纳米管的电子态能级结构分布 仅带来微弱影响．半环葫芦脲分子与碳纳米管在管径方向的一维电子态波函数充分耦合,进而有效改变了一些前沿分子轨道的波函数在管径两头的分布以及相应的电子布居浓度．基于电子输运的模拟,发现半环葫芦脲分子在碳纳米管一维方向滑动时的某个电压下的电导变化可准确反映电子态波函数在相应分子导电通道上的一维分布信息．     

Structures of water molecular nanotube induced by axial tensile strains

Five well-ordered nano-ice structures embedded in carbon nanotubes are obtained in this study. These five nano-ice phases all exhibit single walled tubular morphologies, including the pentagon, hexagon ice nanotubes whose structures are quite different from bulk ice. Our simulation results indicate that water molecules tend to rearrange into surface ring structures to reduce the number of free OH groups. The structural behavior of these ice nanotubes inside CNTs subject to axial stress is also investigated. The ice nanotubes tend to be drawn to ice nanorings or ice nanospring during the mechanical stretching. The distribution function exhibits typical order-to-disorder transition of the water network confined in carbon nanotube during the stretching. By analysis, we suggest that it is unlikely that additional water molecules will enter the tubes because of the increased volume available if the tubes are stretched at contact with a water reservoir.     

Surfactant-nanotube interactions in water and nanotube separation by diameter: atomistic simulations

A non-destructive sorting method to separate single-walled carbon nanotubes (SWNTs) by diameter was recently proposed. By this method, SWNTs are suspended in water by surfactant encapsulation and the separation is carried out by ultracentrifugation in a density gradient. SWNTs of different diameters are distributed according to their densities along the centrifuge tube. A mixture of two anionic surfactants, namely sodium dodecylsulfate (SDS) and sodium cholate (SC), presented the best performance in discriminating nanotubes by diameter. Unexpectedly, small diameter nanotubes are found at the low density part of the centrifuge tube. We present molecular dynamics studies of the water-surfactant-SWNT system to investigate the role of surfactants in the sorting process. We found that surfactants can actually be attracted towards the interior of the nanotube cage, depending on the relationship between the surfactant radius of gyration and the nanotube diameter. The dynamics at room temperature showed that, as the amphiphile moves to the hollow cage, water molecules are dragged together, thereby promoting the nanotube filling. The resulting densities of filled SWNT are in agreement with measured densities.