Three parallel algorithms for classical molecular dynamics are presented. The first assigns each processor a fixed subset of atoms; the second assigns each a fixed subset of inter-atomic forces to compute; the third assigns each a fixed spatial region. The algorithms are suitable for molecular dynamics models which can be difficult to parallelize efficiently—those with short-range forces where the neighbors of each atom change rapidly. They can be implemented on any distributed-memory parallel machine which allows for message-passing of data between independently executing processors. The algorithms are tested on a standard Lennard-Jones benchmark problem for system sizes ranging from 500 to 100,000,000 atoms on several parallel supercomputers--the nCUBE 2, Intel iPSC/860 and Paragon, and Cray T3D. Comparing the results to the fastest reported vectorized Cray Y-MP and C90 algorithm shows that the current generation of parallel machines is competitive with conventional vector supercomputers even for small problems. For large problems, the spatial algorithm achieves parallel efficiencies of 90% and a 1840-node Intel Paragon performs up to 165 faster than a single Cray C9O processor. Trade-offs between the three algorithms and guidelines for adapting them to more complex molecular dynamics simulations are also discussed.

Fast parallel algorithms for short-range molecular dynamics

Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.

The Chemistry and Applications of Metal-Organic Frameworks

Adsorptive separation is very important in industry. Generally, the process uses porous solid materials such as zeolites, activated carbons, or silica gels as adsorbents. With an ever increasing need for a more efficient, energy-saving, and environmentally benign procedure for gas separation, adsorbents with tailored structures and tunable surface properties must be found. Metal–organic frameworks (MOFs), constructed by metal-containing nodes connected by organic bridges, are such a new type of porous materials. They are promising candidates as adsorbents for gas separations due to their large surface areas, adjustable pore sizes and controllable properties, as well as acceptable thermal stability. This critical review starts with a brief introduction to gas separation and purification based on selective adsorption, followed by a review of gas selective adsorption in rigid and flexible MOFs. Based on possible mechanisms, selective adsorptions observed in MOFs are classified, and primary relationships between adsorption properties and framework features are analyzed. As a specific example of tailor-made MOFs, mesh-adjustable molecular sieves are emphasized and the underlying working mechanism elucidated. In addition to the experimental aspect, theoretical investigations from adsorption equilibrium to diffusion dynamics via molecular simulations are also briefly reviewed. Furthermore, gas separations in MOFs, including the molecular sieving effect, kinetic separation, the quantum sieving effect for H2/D2 separation, and MOF-based membranes are also summarized (227 references).

Selective gas adsorption and separation in metal–organic frameworks

1. INTRODUCTION Among the classes of highly porous materials, metalÀorganic frameworks (MOFs) are unparalleled in their degree of tunability and structural diversity as well as their range of chemical and physical properties. MOFs are extended crystalline structures wherein metal cations or clusters of cations (\" nodes \") are connected by multitopic organic \" strut \" or \" linker \" ions or molecules. The variety of metal ions, organic linkers, and structural motifs affords an essentially infinite number of possible combinations. 1 Furthermore, the possibility for postsynthetic modification adds an additional dimension to the synthetic variability. 2 Coupled with the growing library of experimentally determined structures, the potential to computationally predict, with good accuracy, affinities of guests for host frameworks points to the prospect of routinely predesigning frameworks to deliver desired properties. 3,4 MOFs are often compared to zeolites for their large internal surface areas, extensive porosity, and high degree of crystallinity. Correspondingly, MOFs and zeolites have been utilized for many of the same applications

Metal–Organic Framework Materials as Chemical Sensors

Twelve zeolitic imidazolate frameworks (ZIFs; termed ZIF-1 to -12) have been synthesized as crystals by copolymerization of either Zn(II) (ZIF-1 to -4, -6 to -8, and -10 to -11) or Co(II) (ZIF-9 and -12) with imidazolate-type links. The ZIF crystal structures are based on the nets of seven distinct aluminosilicate zeolites: tetrahedral Si(Al) and the bridging O are replaced with transition metal ion and imidazolate link, respectively. In addition, one example of mixed-coordination imidazolate of Zn(II) and In(III) (ZIF-5) based on the garnet net is reported. Study of the gas adsorption and thermal and chemical stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity (Langmuir surface area = 1,810 m 2 /g), high thermal stability (up to 550°C), and remarkable chemical resistance to boiling alkaline water and organic solvents.

https://www.pnas.org/content/pnas/103/27/10186.full.pdf

Exceptional chemical and thermal stability of zeolitic imidazolate frameworks

The long-standing challenge of designing and constructing new crystalline solid-state materials from molecular building blocks is just beginning to be addressed with success. A conceptual approach that requires the use of secondary building units to direct the assembly of ordered frameworks epitomizes this process: we call this approach reticular synthesis. This chemistry has yielded materials designed to have predetermined structures, compositions and properties. In particular, highly porous frameworks held together by strong metal-oxygen-carbon bonds and with exceptionally large surface area and capacity for gas storage have been prepared and their pore metrics systematically varied and functionalized.

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Reticular synthesis and the design of new materials

Covalent organic frameworks (COFs) have been designed and successfully synthesized by condensation reactions of phenyl diboronic acid {C6H4[B(OH)2]2} and hexahydroxytriphenylene [C18H6(OH)6]. Powder x-ray diffraction studies of the highly crystalline products (C3H2BO)6.(C9H12)1 (COF-1) and C9H4BO2 (COF-5) revealed expanded porous graphitic layers that are either staggered (COF-1, P6(3)/mmc) or eclipsed (COF-5, P6/mmm). Their crystal structures are entirely held by strong bonds between B, C, and O atoms to form rigid porous architectures with pore sizes ranging from 7 to 27 angstroms. COF-1 and COF-5 exhibit high thermal stability (to temperatures up to 500 degrees to 600 degrees C), permanent porosity, and high surface areas (711 and 1590 square meters per gram, respectively).

Porous, Crystalline, Covalent Organic Frameworks

The structures of all 1127 three-periodic extended metal−organic frameworks (MOFs) reported in the Cambridge Structure Database have been analyzed, and their underlying topology has been determined. It is remarkable that among the almost infinite number of net topologies that are available for MOFs to adopt, only a handful of nets are actually observed. The discovery of this inversion between expected and observed nets led us to deduce a system of classification “taxonomy” for interpreting and rationalizing known MOF structures, as well as those that will be made in future. The origin of this inversion is attributed to the different modes with which MOF synthesis has been approached. Specifically, three levels of complexity are defined that embody rules “grammar” for the design of MOFs and other extended structures. This system accounts for the present proliferation of MOF structures of high symmetry nets, but more importantly, it provides the basis for designing a building block that “codes” for a specif...

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Reticular Chemistry: Occurrence and Taxonomy of Nets and Grammar for the Design of Frameworks

3.2. Preparation 4090 3.3. Intermediate Layers 4090 3.4. Support 4090 3.5. Modification 4091 3.5.1. Silica Membrane Modification 4091 3.5.2. Membrane Structure Modification 4092 3.6. Operational Stability 4092 4. Zeolite Membranes 4092 4.1. Membrane Growth Methods 4093 4.2. Permeation and Gas Transport 4093 4.3. Defect Site Diffusion/Nonzeolitic Pores 4094 4.4. Thin Films 4094 4.5. Zeolite Membrane Modification 4094 4.6. CO2 Sequestration in H2 Separations 4095 4.7. Manufacturing 4095 5. Carbon-Based Membranes 4096 5.1. Carbon Membrane Preparations 4097 5.2. Carbon Membrane Post-treatment 4097 5.3. Carbon Membrane Module Construction 4097 5.4. Selective Surface Flow Membranes 4097 5.5. Disadvantages of Carbon Membranes 4098 5.6. Molecular Sieving Carbon Membranes 4098 5.7. Carbon Nanotubes 4099 6. Polymer Membranes for H2 Separations 4100 6.1. Dense Polymeric Membranes 4100 6.2. Hydrogen Selective Polymeric Membranes 4101 6.3. H2 versus CO2 Selective Polymeric Membranes 4103

Nathan W. Ockwig

Papers

Reticular synthesis and the design of new materials

Porous, Crystalline, Covalent Organic Frameworks

Reticular Chemistry: Occurrence and Taxonomy of Nets and Grammar for the Design of Frameworks

Membranes for hydrogen separation.

Porous, Crystalline, Covalent Organic Frameworks