Calculating NMR parameters in aluminophosphates : evaluation of dispersion correction schemes

Periodic density functional theory (DFT) calculations have recently emerged as a popular tool for assigning solid-state nuclear magnetic resonance (NMR) spectra. However, in order for the calculations to yield accurate results, accurate structural models are also required. In many cases the structural model (often derived from crystallographic diffraction) must be optimised (i.e., to an energy minimum) using DFT prior to the calculation of NMR parameters. However, DFT does not reproduce weak long-range "dispersion'' interactions well, and optimisation using some functionals can expand the crystallographic unit cell, particularly when dispersion interactions are important in defining the structure. Recently, dispersion-corrected DFT (DFT-D) has been extended to periodic calculations, to compensate for these missing interactions. Here, we investigate whether dispersion corrections are important for aluminophosphate zeolites (AlPOs) by comparing the structures optimised by DFT and DFT-D (using the PBE functional). For as-made AlPOs (containing cationic structure-directing agents (SDAs) and framework-bound anions) dispersion interactions appear to be important, with significant changes between the DFT and DFT-D unit cells. However, for calcined AlPOs, where the SDA-anion pairs are removed, dispersion interactions appear much less important, and the DFT and DFT-D unit cells are similar. We show that, while the different optimisation strategies yield similar calculated NMR parameters (providing that the atomic positions are optimised), the DFT-D optimisations provide structures in better agreement with the experimental diffraction measurements. Therefore, it appears that DFT-D calculations can, and should, be used for the optimisation of calcined and as-made AlPOs, in order to provide the closest agreement with all experimental measurements.PostprintPeer reviewe

Competing interactions in two dimensional Coulomb systems: Surface charge heterogeneities in co-assembled cationic-anionic incompatible mixtures

A binary mixture of oppositely charged components confined to a plane such as cationic and anionic lipid bilayers may exhibit local segregation. The relative strength of the net short range interactions, which favors macroscopic segregation, and the long range electrostatic interactions, which favors mixing, determines the length scale of the finite size or microphase segregation. The free energy of the system can be examined analytically in two separate regimes, when considering small density fluctuations at high temperatures, and when considering the periodic ordering of the system at low temperatures (F. J. Solis and M. Olvera de la Cruz, J. Chem. Phys. 122, 054905 (2000)). A simple Molecular Dynamics simulation of oppositely charged monomers, interacting with a short range Lennard Jones potential and confined to a two dimensional plane, is examined at different strengths of short and long range interactions. The system exhibits well-defined domains that can be characterized by their periodic length-scale as well as the orientational ordering of their interfaces. By adding salt, the ordering of the domains disappears and the mixture macroscopically phase segregates in agreement with analytical predictions.Comment: 8 pages, 5 figures, accepted for publication in J. Chem. Phys, Figure 1 include

On the lack of correlation between Mg II 2796, 2803 Angstrom and Lyman alpha emission in lensed star-forming galaxies

We examine the Mg II 2796, 2803 Angstrom, Lyman alpha, and nebular line emission in five bright star-forming galaxies at 1.66<z<1.91 that have been gravitationally lensed by foreground galaxy clusters. All five galaxies show prominent Mg II emission and absorption in a P Cygni profile. We find no correlation between the equivalent widths of Mg II and Lyman alpha emission. The Mg II emission has a broader range of velocities than do the nebular emission line profiles; the Mg II emission is redshifted with respect to systemic by 100 to 200 km/s. When present, Lyman alpha is even more redshifted. The reddest components of Mg II and Lyman alpha emission have tails to 500-600 km/s, implying a strong outflow. The lack of correlation in the Mg II and Lyman alpha equivalent widths, the differing velocity profiles, and the high ratios of Mg II to nebular line fluxes together suggest that the bulk of Mg II emission does not ultimately arise as nebular line emission, but may instead be reprocessed stellar continuum emission.Comment: The Astrophysical Journal, in press. 6 pages, 2 figure

Theory of dynamic crack branching in brittle materials

The problem of dynamic symmetric branching of an initial single brittle crack propagating at a given speed under plane loading conditions is studied within a continuum mechanics approach. Griffith's energy criterion and the principle of local symmetry are used to determine the cracks paths. The bifurcation is predicted at a given critical speed and at a specific branching angle: both correlated very well with experiments. The curvature of the subsequent branches is also studied: the sign of $T$, with $T$ being the non singular stress at the initial crack tip, separates branches paths that diverge from or converge to the initial path, a feature that may be tested in future experiments. The model rests on a scenario of crack branching with some reasonable assumptions based on general considerations and in exact dynamic results for anti-plane branching. It is argued that it is possible to use a static analysis of the crack bifurcation for plane loading as a good approximation to the dynamical case. The results are interesting since they explain within a continuum mechanics approach the main features of the branching instabilities of fast cracks in brittle materials, i.e. critical speeds, branching angle and the geometry of subsequent branches paths.Comment: 41 pages, 15 figures. Accepted to International Journal of Fractur

Steady-State Cracks in Viscoelastic Lattice Models II

We present the analytic solution of the Mode III steady-state crack in a square lattice with piecewise linear springs and Kelvin viscosity. We show how the results simplify in the limit of large width. We relate our results to a model where the continuum limit is taken only along the crack direction. We present results for small velocity, and for large viscosity, and discuss the structure of the critical bifurcation for small velocity. We compute the size of the process zone wherein standard continuum elasticity theory breaks down.Comment: 17 pages, 3 figure

Some exact results for the velocity of cracks propagating in non-linear elastic models

We analyze a piece-wise linear elastic model for the propagation of a crack in a stripe geometry under mode III conditions, in the absence of dissipation. The model is continuous in the propagation direction and discrete in the perpendicular direction. The velocity of the crack is a function of the value of the applied strain. We find analytically the value of the propagation velocity close to the Griffith threshold, and close to the strain of uniform breakdown. Contrary to the case of perfectly harmonic behavior up to the fracture point, in the piece-wise linear elastic model the crack velocity is lower than the sound velocity, reaching this limiting value at the strain of uniform breakdown. We complement the analytical results with numerical simulations and find excellent agreement.Comment: 9 pages, 13 figure

Steady-State Cracks in Viscoelastic Lattice Models

We study the steady-state motion of mode III cracks propagating on a lattice exhibiting viscoelastic dynamics. The introduction of a Kelvin viscosity $\eta$ allows for a direct comparison between lattice results and continuum treatments. Utilizing both numerical and analytical (Wiener-Hopf) techniques, we explore this comparison as a function of the driving displacement $\Delta$ and the number of transverse sites $N$. At any $N$, the continuum theory misses the lattice-trapping phenomenon; this is well-known, but the introduction of $\eta$ introduces some new twists. More importantly, for large $N$ even at large $\Delta$, the standard two-dimensional elastodynamics approach completely misses the $\eta$-dependent velocity selection, as this selection disappears completely in the leading order naive continuum limit of the lattice problem.Comment: 27 pages, 8 figure

Icosahedral packing of polymer-tethered nanospheres and stabilization of the gyroid phase

We present results of molecular simulations that predict the phases formed by the self-assembly of model nanospheres functionalized with a single polymer "tether", including double gyroid, perforated lamella and crystalline bilayer phases. We show that microphase separation of the immiscible tethers and nanospheres causes confinement of the nanoparticles, which promotes local icosahedral packing that stabilizes the gyroid and perforated lamella phases. We present a new metric for determining the local arrangement of particles based on spherical harmonic "fingerprints", which we use to quantify the extent of icosahedral ordering.Comment: 8 pages, 4 figure