Diquaternary Ammonium Compounds in Zeolite Synthesis: Cyclic and Polycyclic N-Heterocycles Connected by Methylene Chains

An additional dimension has been added to our long-standing studies in high silica zeolite synthesis via a guest/host synergism. We have created and studied the impact of making symmetric diquaternary ammonium compounds, by varying the chain length between nitrogen charge centers, and the heterocycle size and geometry containing the nitrogen. This allows the introduction of a second spatial parameter in the use of the charged organo-cation guest in the zeolite synthesis. The series of 15 diquaternary ammonium compounds (5 heterocycles synthesized onto chain lengths of C4−C6) were tested in a total of 135 zeolite syntheses reactions. Nine screening reactions were employed for each guest molecule, and the conditions built upon past successes in finding novel high silica zeolites via introduction of boron, aluminum, or germanium as substituting tetrahedral framework atoms for silicon. Eighteen different zeolite structures emerged from the studies. The use of specific chain lengths for derivatives of the pyrrolidine ring system produced novel zeolite materials SSZ-74 and 75

Anisotropic dynamics of a vicinal surface under the meandering step instability

We investigate the nonlinear evolution of the Bales-Zangwill instability, responsible for the meandering of atomic steps on a growing vicinal surface. We develop an asymptotic method to derive, in the continuous limit, an evolution equation for the two-dimensional step flow. The dynamics of the crystal surface is greatly influenced by the anisotropy inherent to its geometry, and is characterized by the coarsening of undulations along the step direction and by the elastic relaxation in the mean slope direction. We demonstrate, using similarity arguments, that the coalescence of meanders and the step flow follow simple scaling laws, and deduce the exponents of the characteristic length scales and height amplitude. The relevance of these results to experiments is discussed.Comment: 10 pages, 7 figures; submitted to Phys. Rev.

A Most Unusual Zeolite Templating: Cage to Cage Connection of One Guest Molecule

An unusual case of a diquaternary ammonium dication, with large bulky end groups built from the tropane moiety and connected by a C4 methylene chain, is found to reside in zeolite SSZ-35 (STF). The structure of the guest/host product is such that the tropane bicylic entities reside in the shallow cavities of the cages of the STF structure and the C4 methylene chain runs through the 10-ring (~5.5 Å) window that connects the cages. This is a most unusual (and energy-intensive) templating of a zeolite structure with the guest molecule spanning two unit cells. The unusual result was found by single crystal studies with the addition of the use of the SQUEEZE program to show a consistent fit for the guest molecule following from measured electron densities in the crystal structure work. These analyses were followed with MAS NMR studies to confirm the integrity of the diquaternary guest molecule in the host sieve. A few comparative diquaternary guest molecules in MFI zeolite are also studied

Lattice Effects in Crystal Evaporation

We study the dynamics of a stepped crystal surface during evaporation, using the classical model of Burton, Cabrera and Frank, in which the dynamics of the surface is represented as a motion of parallel, monoatomic steps. The validity of the continuum approximation treated by Frank is checked against numerical calculations and simple, qualitative arguments. The continuum approximation is found to suffer from limitations related, in particular, to the existence of angular points. These limitations are often related to an adatom detachment rate of adatoms which is higher on the lower side of each step than on the upper side ("Schwoebel effect").Comment: DRFMC/SPSMS/MDN, Centre d'Etudes Nucleaires de Grenoble, 25 pages, LaTex, revtex style. 8 Figures, available upon request, report# UBFF30119

Physicochemical Properties and Catalytic Behavior of the Molecular Sieve SSZ-70

SSZ-70 is synthesized using 1,3-bis(isobutyl)imidazolium, 1,3-bis(cyclohexyl)imidazolium, and 1,3-bis(cycloheptyl)imidazolium structure directing agents (SDAs), and the solids obtained are characterized by powder X-ray diffraction (XRD), ^(29)Si magic angle spinning nuclear magnetic resonance (MAS NMR), electron microscopy, nitrogen and hydrocarbon adsorption, and thermogravimetric analyses. The physicochemical properties of SSZ-70 show that it is a new molecular sieve that has similarities to MWW-type materials. The catalytic behavior of SSZ-70 is evaluated through the use of the constraint index (CI) test. Distinct differences in the reactivity between Al-SSZ-70 and SSZ-25 (MWW) are observed and are the consequences of the structural differences between these two molecular sieves

Spiral Evolution in a Confined Geometry

Supported nanoscale lead crystallites with a step emerging from a non-centered screw dislocation on the circular top facet were prepared by rapid cooling from just above the melting temperature. STM observations of the top facet show a nonuniform rotation rate and shape of the spiral step as the crystallite relaxes. These features can be accurately modeled using curvature driven dynamics, as in classical models of spiral growth, with boundary conditions fixing the dislocation core and regions of the step lying along the outer facet edge.Comment: 4 pages, 3 figures, to be published in Physical Review Letter

Using network-flow techniques to solve an optimization problem from surface-physics

The solid-on-solid model provides a commonly used framework for the description of surfaces. In the last years it has been extended in order to investigate the effect of defects in the bulk on the roughness of the surface. The determination of the ground state of this model leads to a combinatorial problem, which is reduced to an uncapacitated, convex minimum-circulation problem. We will show that the successive shortest path algorithm solves the problem in polynomial time.Comment: 8 Pages LaTeX, using Elsevier preprint style (macros included

Isolated X-ray -- infrared sources in the region of interaction of the supernova remnant IC 443 with a molecular cloud

The nature of the extended hard X-ray source XMMU J061804.3+222732 and its surroundings is investigated using XMM-Newton, Chandra, and Spitzer observations. This source is located in an interaction region of the IC 443 supernova remnant with a neighboring molecular cloud. The X-ray emission consists of a number of bright clumps embedded in an extended structured non-thermal X-ray nebula larger than 30" in size. Some clumps show evidence for line emission at ~1.9 keV and ~3.7 keV at the 99% confidence level. Large-scale diffuse radio emission of IC 443 passes over the source region, with an enhancement near the source. An IR source of about 14" x 7" size is prominent in the 24 um, 70 um, and 2.2 um bands, adjacent to a putative Si K-shell X-ray line emission region. The observed IR/X-ray morphology and spectra are consistent with those expected for J/C-type shocks of different velocities driven by fragmented supernova ejecta colliding with the dense medium of a molecular cloud. The IR emission of the source detected by Spitzer can be attributed to both continuum emission from an HII region created by the ejecta fragment and line emission excited by shocks. This source region in IC 443 may be an example of a rather numerous population of hard X-ray/IR sources created by supernova explosions in the dense environment of star-forming regions. Alternative Galactic and extragalactic interpretations of the observed source are also discussed.Comment: The Astrophysical Journal, v. 677 (April 2008), in pres

Boundary element method for resonances in dielectric microcavities

A boundary element method based on a Green's function technique is introduced to compute resonances with intermediate lifetimes in quasi-two-dimensional dielectric cavities. It can be applied to single or several optical resonators of arbitrary shape, including corners, for both TM and TE polarization. For cavities with symmetries a symmetry reduction is described. The existence of spurious solutions is discussed. The efficiency of the method is demonstrated by calculating resonances in two coupled hexagonal cavities.Comment: 9 pages, 7 figures (quality reduced