Separation of hydrocarbon mixture of neopentane and n-hexane using NaY zeolite: Large distinct diffusivity.

A recently proposed method based on Levitation and Blow torch effects, is employed here to see if it can separate a mixture of neopentane and n-hexane. The results show that the mixture can be separated with a hot zone temperature of just 40 K above the ambient temperature, 300 K. The two components are found to accumulate at the two extreme ends of the zeolite column. The computed separation factor is in the range of 1015 -1020 (as compared to 104 for existing separation methods). The energy expense for the separation is significantly smaller than for existing separation methods by several orders of magnitude. Transport (D11 ), self (Ds ), and distinct diffusivities (Dd ) of the mixture were computed. The contribution of distinct diffusivity to the transport diffusivity is 70% as compared to 10%-30% seen in other separation methods and is larger by 2.3 times as compared to the self-diffusivity.

High purity separation of n-pentane from neopentane using a nano-crystal of zeolite Y.

A method for the separation of a mixture of n-pentane and neopentane using a nano-crystallite of zeolite Y is reported. This method judiciously combines two well-known, counter-intuitive phenomena, the levitation and the blowtorch effects. The result is that the two components are separated by being driven to the opposite ends of the zeolite column. The calculations are based on the non-equilibrium Monte Carlo method with moves from a region at one temperature to a region at another temperature. The necessary acceptance probability for such moves has been derived here on the basis of stationary solution of an inhomogeneous Fokker-Planck equation. Simulations have been carried out with a realistic and experimentally relevant Gaussian hot zone and also a square hot zone, both of which lead to very good separation. Simulations without the hot zones do not show any separation. The results are reported at a loading of 1 molecule per cage. The temperature of the hot zone is just ∼30 K higher than the ambient temperature. The separation factors of the order of 1017 are achieved using single crystals of zeolite, which are less than 1 µm long. The conditions for including the hot zone may be experimentally realizable in the future considering the rapid advances in nanoscale thermometry. The separation process is likely to be energetically more efficient by several orders of magnitude as compared to the existing methods of separation, making the method very green.

Shared hydrogen bonds: water in aluminated faujasite.

Water confined in faujasite, a zeolite, with aluminium content, exhibits properties different from those of bulk water as well as water confined in siliceous faujasite. The RDF between oxygen of water (OW) and oxygen of aluminium (OAl) shows a prominent first peak near to 2.9 Å similar to any oxygen-oxygen RDF seen in bulk water and unlike water confined in siliceous faujasite. Further, HW-OAl shows a peak near 1.9 Å suggesting hydrogen bonding between hydrogen of water and OAl. The water satisfies the hydrogen bond criteria with both O1Al and O2Al indicating that it is participating in a shared hydrogen bond. The hydrogen bond exchange between such a water forming a shared hydrogen bond to OAl and another water molecule H2Ob is investigated through the changes in the distances and appropriate angles. The O-Al-O angle of the zeolite increases by about 7 degrees on the formation of the shared hydrogen bond. The jump dynamics of the shared hydrogen bond when the two bonds break simultaneously has been obtained and this is reported. This jump reorientation dynamics is different compared to normal hydrogen bonding reported by Laage and Hynes: it has a short lifetime, around 50-100 fs computed from SHB(t). The intermittent and continuous hydrogen bond correlation functions are also reported.

High Interfacial Barriers at Narrow Carbon Nanotube-Water Interfaces.

Water displays anomalous fast diffusion in narrow carbon nanotubes (CNTs), a behavior that has been reproduced in both experimental and simulation studies. However, little is reported on the effect of bulk water-CNT interfaces, which is critical to exploiting the fast transport of water across narrow carbon nanotubes in actual applications. Using molecular dynamics simulations, we investigate here the effect of such interfaces on the transport of water across arm-chair CNTs of different diameters. Our results demonstrate that diffusion of water is significantly retarded in narrow CNTs due to bulk regions near the pore entrance. The slowdown of dynamics can be attributed to the presence of large energy barriers at bulk water-CNT interfaces. The presence of such intense barriers at the bulk-CNT interface arises due to the entropy contrast between the bulk and confined regions, with water molecules undergoing high translational and rotational entropy gain on entering from the bulk to the CNT interior. The intensity of such energy barriers decreases with increase in CNT diameter. These results are very important for emerging technological applications of CNTs and other nanoscale materials, such as in nanofluidics, water purification, nanofiltration, and desalination, as well as for biological transport processes.

Diffusion processes in a poly-crystalline zeolitic material: A molecular dynamics study.

Extensive molecular dynamics simulations of xenon in two classes of zeolite crystal systems, one consisting of purely intra-crystalline space and the other with both intra- and inter-crystalline space are reported. The latter mimics a typical poly-crystalline sample of zeolite. Comparison of results from these two systems provides insights into the structure and dynamics in the presence of inter-crystalline space. The temperature, as well as the distance between the crystallites, has been varied. The density distribution and diffusivities calculated inside the poly-crystalline system show that the interfacial region between the crystal and the inter-crystalline region acts as a bottleneck for diffusion through the system. At lower temperatures, the particles are trapped at the interface due to the pronounced energy minima present in that region. With the increase in temperature, the particles are able to overcome this barrier frequently, and the transport across the inter-crystalline region is increased. A ballistic or superdiffusive motion is seen in the inter-crystalline region along all the axes except along the axis which has the inter-crystalline space. The transition time for ballistic to diffusive motion increases with the increase in the length of the inter-crystalline space. Velocity auto- and cross correlation functions exhibit strong oscillations and exchange of kinetic energy along directions perpendicular to the direction of the inter-crystalline space. These results explain why uptake and PFG-NMR measurements exhibit lower values for diffusivity for the same system when compared to Quasi-Elastic Neutron Scattering. Thus, using molecular dynamics simulations, we were able to correlate the difference of diffusivity values measured using various experimental methods where these inter-crystalline regions are common.

A molecular dynamics study of ambient and high pressure phases of silica: structure and enthalpy variation with molar volume.

Extensive molecular dynamics studies of 13 different silica polymorphs are reported in the isothermal-isobaric ensemble with the Parrinello-Rahman variable shape simulation cell. The van Beest-Kramer-van Santen (BKS) potential is shown to predict lattice parameters for most phases within 2%-3% accuracy, as well as the relative stabilities of different polymorphs in agreement with experiment. Enthalpies of high-density polymorphs - CaCl2-type, α-PbO2-type, and pyrite-type - for which no experimental data are available as yet, are predicted here. Further, the calculated enthalpies exhibit two distinct regimes as a function of molar volume-for low and medium-density polymorphs, it is almost independent of volume, while for high-pressure phases a steep dependence is seen. A detailed analysis indicates that the increased short-range contributions to enthalpy in the high-density phases arise not only from an increased coordination number of silicon but also shorter Si-O bond lengths. Our results indicate that amorphous phases of silica exhibit better optimization of short-range interactions than crystalline phases at the same density while the magnitude of Coulombic contributions is lower in the amorphous phase.

Effect of pressure on the ionic conductivity of Li+ and Cl- ions in water.

A molecular dynamics simulation study of aqueous solution of LiCl is reported as a function of pressure. Experimental measurements of conductivity of Li(+) ion as a function of pressure shows an increase in conductivity with pressure. Our simulations are able to reproduce the observed trend in conductivity. A number of relevant properties have been computed in order to understand the reasons for the increase in conductivity with pressure. These include radial distribution function, void and neck distributions, hydration or coordination numbers, diffusivity, velocity autocorrelation functions, angles between ion-oxygen and dipole of water as well as OH vector, mean residence time for water in the hydration shell, etc. These show that the increase in pressure acts as a structure breaker. The decay of the self part of the intermediate scattering function at small wave number k shows a bi-exponential decay at 1 bar which changes to single exponential decay at higher pressures. The k dependence of the ratio of the self part of the full width at half maximum of the dynamic structure factor to 2Dk(2) exhibits trends which suggest that the void structure of water is playing a role. These support the view that the changes in void and neck distributions in water can account for changes in conductivity or diffusivity of Li(+) with pressure. These results can be understood in terms of the levitation effect.

Mutual Diffusivity of an n-Hexane-2,2-Dimethyl Butane Binary Mixture Confined to Zeolite Y.

A molecular dynamic study of a mixture of n-hexane and 2,2-dimethyl butane (22DMB) confined to zeolite NaY has been carried out to understand the distinct diffusivity and mutual diffusivity. Results have been compared with the bulk mixture. For each of these mixtures, eight different runs were employed to compute distinct and mutual diffusivity. From the velocity auto- and cross-correlation functions between n-hexane and n-hexane, n-hexane and 22DMB, 22DMB and 22DMB, the self- and distinct diffusivity of the mixture has been computed. The thermodynamic factor and mutual diffusivity have been calculated. The ratio of D11 to Ds is seen to be 1.11 and 0.75 for the confined mixture, while they are 1.21 and 0.79 for the bulk mixture at 200 and 300 K, respectively.

Understanding Translational-Rotational Coupling in Liquid Water through Changes in Mass Distribution.

A molecular dynamics study of liquid water and models of water has been carried out to understand the effect of changes in the mass distribution on molecular translation and rotation. Calculations on the motion of mH2O and H2nO, where m and n vary over a range of values by varying the mass at the hydrogen and oxygen positions, show that these form two distinct series. The two series exhibit different translational and rotational properties. Although a decrease in diffusivity when compared to H2O is observed in both the series, in the case of mH2O series, an enhancement in the ratio of diffusivities {D[H2O]/D[mH2O]} is found as compared to the square root of the inverse mass ratios, whereas the effect of mass distribution for H2nO is seen to lead to a reduction in the ratio of diffusivities {D[H2O]/D[H2nO]} with respect to the square root of the inverse mass ratios. However, the ratios of diffusivities in both the series deviate from the corresponding mass ratios, which can be attributed to the translation-rotation coupling in liquid water.

Concentration Dependent Self-Assembly of TrK-NGF Receptor Derived Tripeptide: New Insights from Experiment and Computer Simulations.

Early research has shown that many neurodegenerative diseases are associated with the absence of a short and natural tripeptide sequence, Lys-Phe-Gly (KFG). Herein we report results of both experiments and extensive MD simulations of this tripeptide to understand the self-assembly and morphology as a function of its concentration. Morphologies of the aggregates formed by the tripeptide at low concentration (vesicles), and at high concentration (nanotubes) are studied by several independent 3 µs long Martini coarse-graining MD simulation runs. Further, prediction from MD at still higher concentrations about the formation of rectangular blocks, reported for the first time, has been verified through laboratory experiments. Thus, the computational studies performed are in agreement with the experimental findings observed in our laboratory and a complete control over the formation of various nanostructures is achieved simply by changing the concentration of a short and naturally conserved tripeptide.