Structure, energetics and diffusion properties of isomers of trimethyl benzene in beta zeolite: Uptake and Monte Carlo simulation study

A Monte Carlo study along with experimental uptake measurements of 1,2,3-trimethyl benzene, 1,2,4-trimethyl benzene and 1,3,5-trimethyl benzene (TMB) in beta zeolite is reported. The TraPPE potential has been employed for hydrocarbon interaction and harmonic potential of Demontis for modeling framework of the zeolite. Structure, energetics and dynamics of TMB in zeolite beta from Monte Carlo runs reveal interesting information about the diameter, properties of these isomers on confinement. Of the three isomers, 135TMB is supposed to have the largest diameter. It is seen TraPPE with Demontis potential predicts a restricted motion of 135TMB in the channels of zeolite beta.Experimentally, 135TMB has the highest transport diffusivity whereas MID results suggest this has the lowest self diffusivity. (C) 2009 Elsevier Inc. Ail rights reserved.

A comparative molecular dynamics study of diffusion of n-decane and 3-methyl pentane in Y zeolite

Molecular dynamics simulations are reported on the structure and dynamics of n-decane and 3-methylpentane in zeolite NaY. We have calculated several properties such as the center of mass-center of mass rdf, the end-end distance distribution, bond angle distribution and dihedral angle distribution. We have also analysed trajectory to obtain diffusivity and velocity autocorrelation function (VACF). Surprisingly, the diffusivity of 3-methylpentane which is having larger cross-section perpendicular to the long molecular axis is higher than n-decane at 300 K. Activation energies have been obtained from simulations performed at 200 K, 300 K, 350 K, 400 K and 450 K in the NVE ensemble. These results can be understood in terms of the previously known levitation effect. Arrhenious plot has higher value of slope for n-decane (5 center dot 9 kJ/mol) than 3-methylpentane (3 center dot 7 kJ/mol) in agreement with the prediction of levitation effect.

Levitation effect in zeolites: Quasielastic neutron scattering and molecular dynamics study of pentane isomers in zeolite NaY

We report the quasielastic neutron scattering (QENS) and molecular dynamics (MD) investigations into diffusion of pentane isomers in zeolite NaY. The molecular cross section perpendicular to the long molecular axis varies for the three isomers while the mass and the isomer-zeolite interaction remains essentially unchanged. Both QENS and MD results show that the branched isomers neopentane and isopentane have higher self-diffusivities as compared with n-pentane at 300 K in NaY zeolite. This result provides direct experimental evidence for the existence of nonmonotonic, anomalous dependence of self-diffusivity on molecular diameter known as the levitation effect. The energetic barrier at the bottleneck derived from MD simulations exists for n-pentane which lies in the linear regime while no such barrier is seen for neopentane which is located clearly in the anomalous regime.Activation energy is in the order E-a(n-pentane)>E-a(isopentane)>E-a(neopentane) consistent with the predictions of the levitation effect. In the liquid phase, it is seen thatD(n pentane)>D(isopentane)>D(neopentane) and E-a(n-pentane)< E-a(isopentane)< E-a(neopentane). Intermediate scattering function for small wavenumbers obtained from MD follows a single exponential decay for neopentane and isopentane. For n-pentane, a single exponential fit provides a poor fit especially at short times. Cage residence time is largest for n-pentane and lowest for neopentane. For neopentane, the width of the self-part of the dynamic structure factor shows a near monotonic decrease with wavenumber. For n-pentane a minimum is seen near k=0.5 A degrees(-1) suggesting a slowing down of motion around the 12-ring window, the bottleneck for diffusion. Finally, the result that the branched isomer has a higher diffusivity as compared with the linear analog is at variation from what is normally seen.

A molecular dynamics study of cage-to-cage migration in sodium Y zeolite: role of surface-mediated diffusion

The details of cage-to-cage migration have been obtained from an analysis of the molecular dynamics trajectory of a probe adsorbate. It is observed that particles utilize the region within a radius of 2 angstrom from the window center but with diffusion taking place predominantly at 1.6 angstrom from the window center and a potential energy of nearly -12 kJ/mol. A barrier of about 0.5 kJ/mol is observed for surface-mediated diffusion. Surprisingly, for diffusion without surface mediation for a particle going from one cage center to another, there is an attractive well near the window instead of a barrier. At low adsorbate concentrations and room temperature, the predominant mode for cage-to-cage migration is surface-mediated diffusion. The analysis suggests that particles slide along the surface of the inner walls of the alpha-cages during migration from one cage to another.

Effect of Sorbate-Zeolite Interaction on Cluster Lifetime and Size of Sorbates: Xe in NaY

Molecular dynamics calculations are reported for Xe in sodium Y zeolite with varying strengths of sorbate-zeolite dispersion interaction. In the absence of any dispersion interaction between the sorbate and the zeolite, the presence of the zeolite has a purely geometrical role. Increase in the strength of the sorbate-zeolite interaction increases the monomer population and decreases the population of dimers and higher sized clusters. The lifetime of the monomers as well as dimers increases with the strength of the dispersion interaction. The observed variations in the lifetime and the population of the different sized clusters is explained in terms of the changes in the potential energy surface caused by the increase in the strength of the dispersion interaction.

Influence of non-geometrical factors on intracrystalline diffusion -- Role of sorbate-zeolite interactions

Molecular dynamics simulations on Xe in NaY and Ar in NaCaA zeolite are reported. Rates of cage-to-cage crossovers in the two zeolites exhibit trends which are contrary to that expected from geometrical considerations. The results suggest the important role of the sorbate-zeolite interactions in determining the molecular sieve properties of zeolites for small sized sorbates. The results are explained in terms of the barrier height for cage-to-cage crossover in the two zeolites.

Parallel Tempering Simulations of Liquid-Phase Adsorption of n-Alkane Mixtures in Zeolite LTA-5A

Adsorption of n-alkane mixtures in the zeolite LTA-5A under liquid-phase conditions has been studied using grand canonical Monte Carlo (GCMC) simulations combined with parallel tempering. Normal GCMC techniques fail for some of these systems due to the preference of linear molecules to coil within a single cage in the zeolite. The narrow zeolite windows severerly restrict interactions of the molecules, making it difficult to simulate cooperative rearrangements necessary to explore configuration space. Because of these reasons, normal GCMC simulations results show poor reproducibility in some cases. These problems were overcome with parallel tempering techniques. Even with parallel tempering, these are very challenging systems for molecular simulation. Similar problems may arise for other zeolites such as CHA, AFX, ERI, KFI, and RHO having cages connected by narrow windows. The simulations capture the complex selectivity behavior observed in experiments such as selectivity inversion and azeotrope formation.

Dynamics of zeolite cage and its effect on the diffusion properties of sorbate: persistence of diffusion anomaly in NaA zeolite

Recent computer simulations on zeolites Y and A have found that the diffusion coefficient and the rate of intercage diffusion exhibit, apart from a linear dependence on the reciprocal of the square of the sorbate diameter, an anomalous peak as sorbate diameter approaches the window diameter. Here we report molecular dynamics simulations of zeolite NaA incorporating framework flexibility as a function of sorbate diameter in order to verify the existence of anomalous diffusion. Results suggest persistence of anomalous diffusion or ring effect. This suggests that the anomalous behavior is a general effect characteristic of zeolites Y and A. The barrier for diffusion across the eight-ring window is seen to be negative and is found to decrease with sorbate size. The effect of sorbate on the cage motion has also been investigated. Results suggest that the window expands during intercage migration only if the sorbate size is comparable to the window diameter. Flexible cage simulations yield a higher value for the diffusion coefficient and also the rate of intercage diffusion. This increase has been shown to be due to an increase in the intercage diffusions via the centralized diffusion mode rather than the surface-mediated mode. It is shown that this increase arises from an increase in the single particle density distribution in the region near the cage center.

Xenon in sodium Y zeolite. 2. Arrhenius relation, mechanism, and barrier height distribution for cage-to-cage diffusion

Various geometrical and energetic distribution functions and other properties connected with the cage-to-cage diffusion of xenon in sodium Y zeolite have been obtained from long molecular dynamics calculations. Analysis of diffusion pathways reveals two interesting mechanisms-surface-mediated and centralized modes for cage-to-cage diffusion. The surface-mediated mode of diffusion exhibits a small positive barrier, while the centralized diffusion exhibits a negative barrier for the sorbate to diffuse across the 12-ring window. In both modes, however, the sorbate has to be activated from the adsorption site to enable it to gain mobility. The centralized diffusion additionally requires the sorbate to be free of the influence of the surface of the cage as well. The overall rate for cage-to-cage diffusion shows an Arrhenius temperature dependence with E(a) = 3 kJ/mol. It is found that the decay in the dynamical correction factor occurs on a time scale comparable to the cage residence time. The distributions of barrier heights have been calculated. Functions reflecting the distribution of the sorbate-zeolite interaction at the window and the variations of the distance between the sorbate and the centers of the parent and daughter cages are presented.

Molecular dynamics investigation of sorption of argon in NaCaA zeolite

A molecular dynamics calculation of argon in NaCaA zeolite at 393 K and 1 atom per cage is reported. Equilibrium properties such as guest-host interaction energy, guest-guest dimerization and bonding energy, various guest-host and guest-guest radial distribution functions and dynamical properties such as the mean-square displacement, power spectra and diffusion coefficient have been obtained.

Inverse surface melting in confined clusters: Ar-13 in zeolite L

Monte Carlo and molecular dynamics simulations on an Ar-13 cluster in zeolite L have been carried out at a series of temperatures to understand the rigid-nonrigid transition corresponding to the solid-liquid transition exhibited by the free Ar-13 cluster. The icosahedral geometry of the free cluster is no longer preferred when the cluster is confined in the zeolite. The root-mean-squared pair distance fluctuation, delta, exhibits a sharp, well-defined rigid-nonrigid transition at 17 K as compared to 27 K for the free cluster. Multiple peaks in the distribution of short-time averages of the guest-host interaction energy indicate coexistence of two phases.; It is shown that this transition is associated with the inner atoms becoming mobile at 17 K even while the outer layer atoms, which are in close proximity to the zeolitic wall, continue to be comparatively immobile. This may be contrasted with the melting of large free clusters of 40 or more atoms which exhibit surface melting. Guest-host interactions seem to play a predominant role in determining the properties of confined clusters. We demonstrate that the volume of the cluster increases rather sharply at 17 and 27 K respectively for the confined and the free cluster. Power spectra suggest that the motion of the inner atoms is generally parallel to the atoms which form the cage wall.

Mean field lattice model for adsorption isotherms in zeolite NaA

Using a lattice model for adsorption in microporous materials, pure component adsorption isotherms are obtained within a mean field approximation for methane at 300 K and xenon at 300 and 360 K in zeolite NaA. It is argued that the increased repulsive adsorbate-adsorbate interactions at high coverages must play an important role in determining the adsorption behavior. Therefore, this feature is incorporated through a "coverage-dependent interaction'' model, which introduces a free, adjustable parameter. Another important feature, the site volume reduction, has been treated in two ways: a van der Waal model and a 1D hard-rod theory [van Tassel et al., AIChE J. 40, 925 (1994)]; we have also generalized the latter to include all possible adsorbate overlap scenarios. In particular, the 1D hard-rod model, with our coverage-dependent interaction model, is shown to be in best quantitative agreement with the previous grand canonical Monte Carlo isotherms. The expressions for the isosteric heats of adsorption indicate that attractive and repulsive adsorbate-adsorbate interactions increase and decrease the heats of adsorption, respectively. It is concluded that within the mean field approximation, our simple model for repulsive interactions and the 1D hard-rod model for site volume reduction are able to capture most of the important features of adsorption in confined regions. (C) 1999 American Institute of Physics. [S0021-9606(99)70515-5].

Direct and sensitized (energy and electron transfer) geometric isomerization of stilbene within zeolites: a comparison between solution and zeolite as reaction media

The trans- and cis-stilbenes upon inclusion in NaY zeolite are thermally stable. Direct excitation and triplet sensitization results in geometric isomerization and the excited state behavior under these conditions are similar to that in solution. Upon direct excitation, a photostationary state consisting of 65% cis and 35% trans isomers is established. Triplet sensitization with 2-acetonaphthone gave a photostationary state consisting of 63% cis and 37% trans isomers. These numbers are similar to the ones obtained in solution. Thus, the presence of cations and the confined space within the zeolite have very little influence on the overall chemistry during direct and triplet sensitization. However, upon electron transfer sensitization with N-methylacridinium (NMA) as the sensitizer within NaY, isomerization from cis-stilbene radical cation to trans-stilbene occurs and the recombination of radical ions results in triplet stilbene. Prolonged irradiation gave a photostationary state (65% cis and 35% trans) similar to triplet sensitization. This behavior is unique to the zeolite and does not take place in solution. Steady state fluorescence measurements showed that the majority of stilbene molecules are close to the N-methylacridinium sensitizer. Diffuse reflectance flash photolysis studies established that independent of the isomer being sensitized only trans radical cation is formed. Triplet stilbene is believed to be generated via recombination of stilbene radical cation and sensitizer radical anion. One should be careful in using acidic HY zeolite as a medium for photoisomerization of stilbenes. In our hands, in these acidic zeolites isomerization dominated the photoisomerization. (C) 2002 Elsevier Science B.V. All rights reserved.

Encapsulation of cobalt phthalocyanine in zeolite-Y: Evidence for nonplanar geometry

Cobalt (11) phthalocyanine (CoPc) molecules have been encapsulated within the supercage of zeolite-Y. The square-planar complex, being larger than the almost spherical cage, is forced to adopt a distorted geometry on encapsulation. A comparative spectroscopic and magnetic investigation of CoPc encapsulated in zeolite-Y and in the unencapsulated state is reported. These results supported by molecular modeling have been used to understand the nature and extent of the loss of planarity of CoPc on encapsulation. The encapsulated molecule is shown to be the trans-diprotonated species in which the center of inversion is lost due to distortions required to accommodate the square complex within the zeolite. Encapsulation also leads to an enhancement of the magnetic moment of the CoPc. This is shown to be a consequence of the nonplanar geometry of the encapsulated molecule resulting in an excited high-spin state being thermally accessible.

Alkylation of toluene by methanol over alkali exchanged zeolite-X: side chain versus ring alkylation

The ring versus side-chain alkylation of toluene with methanol over alkali-exchanged zeolite-X of differing basicity has been investigated by in situ infrared spectroscopy and TPD measurements. Over the basic Cs-exchanged zeolite the product of alkylation is styrene/ethylbenzene while over the acidic Li-exchanged zeolite ring alkylation occurs to give mainly xylene as the product. FTIR and TPD investigations reveal that, the key difference in the two types of alkylation processes lies in the state of the adsorbed methanol present at higher temperatures in the zeolite. In basic zeolites, methanol decomposes to formaldehyde and formates. The former is the key ‘side-chain’ alkylating species that leads to the formation of styrene. In the acidic zeolites it is shown that methanol bound to the acid sites plays an active role in the ‘ring alkylation’ of toluene to xylene.