Grand canonical Monte Carlo (GCMC) simulations were performed to investigate hydrogen sorption in an rht-type metal−organic framework (MOF), PCN-61. The MOF was shown to have a large hydrogen uptake, and this was studied using three different hydrogen potentials, effective for bulk hydrogen, but of varying sophistication: a model that includes only repulsion/dispersion parameters, one augmented with charge-quadrupole interactions, and one supplemented with many-body polarization interactions. Calculated hydrogen uptake isotherms and isosteric heats of adsorption, Q st , were in quantitative agreement with experiment only for the model with explicit polarization. This success in reproducing empirical measurements suggests that modeling MOFs that have open metal sites is feasible, though it is often not considered to be well described via a classical potential function; here it is shown that such systems may be accurately described by explicitly including polarization effects in an otherwise traditional empirical potential. Decomposition of energy terms for the models revealed deviations between the electrostatic and polarizable results that are unexpected due to just the augmentation of the potential surface by the addition of induction. Charge-quadrupole and induction energetics were shown to have a synergistic interaction, with inclusion of the latter resulting in a significant increase in the former. Induction interactions strongly influence the structure of the sorbed hydrogen compared to the models lacking polarizability; sorbed hydrogen is a dipolar dense fluid in the MOF. This study demonstrates that many-body polarization makes a critical contribution to gas sorption structure and must be accounted for in modeling MOFs with polar interaction sites.

Monte Carlo simulations were performed modeling hydrogen sorption in a recently synthesized metal-organic framework material (MOF) that exhibits large molecular hydrogen uptake capacity. The MOF is remarkable because at 78 K and 1.0 atm it sorbs hydrogen at a density near that of liquid hydrogen (at 20 K and 1.0 atm) when considering H2 density in the pores. Unlike most other MOFs that have been investigated for hydrogen storage, it has a highly ionic framework and many relatively small channels. The simulations demonstrate that it is both of these physical characteristics that lead to relatively strong hydrogen interactions in the MOF and ultimately large hydrogen uptake. Microscopically, hydrogen interacts with the MOF via three principle attractive potential energy contributions: Van der Waals, charge-quadrupole, and induction. Previous simulations of hydrogen storage in MOFs and other materials have not focused on the role of polarization effects, but they are demonstrated here to be the dominant contribution to hydrogen physisorption. Indeed, polarization interactions in the MOF lead to two distinct populations of dipolar hydrogen that are identified from the simulations that should be experimentally discernible using, for example, Raman spectroscopy. Since polarization interactions are significantly enhanced by the presence of a charged framework with narrow pores, MOFs are excellent hydrogen storage candidates.

An anisotropic many-body H2 potential energy function has been developed for use in heterogeneous systems. The intermolecular potential has been derived from first principles and expressed in a form that is readily transferred to exogenous systems, e.g. in modeling H2 sorption in solid-state materials. Explicit many-body polarization effects, known to be important in simulating hydrogen at high density, are incorporated. The analytic form of the potential energy function is suitable for methods of statistical physics, such as Monte Carlo or Molecular Dynamics simulation. The model has been validated on dense supercritical hydrogen and demonstrated to reproduce the experimental data with high accuracy.

Grand canonical Monte Carlo simulations of H2 sorption were performed in the metal–organic framework rht-MOF-1. The binding sites were revealed by combining simulation and inelastic neutron scattering data.

Newly developed hydrogen and MOM (Metal-Organic Materials) potential energy functions for molecular simulation are presented. They are designed to be highly transferable while still describing sorbate-MOM interactions with predictive accuracy. Specifically, they are shown to quantitatively describe hydrogen sorption, including isosteric heats, in MOF-5 over the broad temperature and pressure ranges that have been examined experimentally. The approach that is adopted is general and demonstrates that highly accurate and predictive models of molecular interaction with MOMs are quite feasible. Molecular interactions giving rise to the isosteric heat have been characterized and validated against the experimentally relevant data. Finally, inspection of the isothermal compressibility of hydrogen in MOF-5 reveals that under saturating high-pressure conditions (even at temperatures well above the neat boiling point) the state of hydrogen is characteristic of a liquid, i.e., with a compressibility similar to that of bulk hydrogen. This result is of particular relevance in developing MOMs for hydrogen-storage applications.

We report rigorous quantum five-dimensional (5D) calculations of the coupled translation-rotation (T-R) eigenstates of a H(2) molecule adsorbed in metal organic framework-5 (MOF-5), a prototypical nanoporous material, which was treated as rigid. The anisotropic interactions between H(2) and MOF-5 were represented by the analytical 5D intermolecular potential energy surface (PES) used previously in the simulations of the thermodynamics of hydrogen sorption in this system [Belof et al., J. Phys. Chem. C 113, 9316 (2009)]. The global and local minima on this 5D PES correspond to all of the known binding sites of H(2) in MOF-5, three of which, α-, β-, and γ-sites are located on the inorganic cluster node of the framework, while two of them, the δ- and ε-sites, are on the phenylene link. In addition, 2D rotational PESs were calculated ab initio for each of these binding sites, keeping the center of mass of H(2) fixed at the respective equilibrium geometries; purely rotational energy levels of H(2) on these 2D PESs were computed by means of quantum 2D calculations. On the 5D PES, the three adjacent γ-sites lie just 1.1 meV above the minimum-energy α-site, and are separated from it by a very low barrier. These features allow extensive wave function delocalization of even the lowest translationally excited T-R eigenstates over the α- and γ-sites, presenting significant challenges for both the quantum bound-state calculations and the analysis of the results. Detailed comparison is made with the available experimental data.

We have performed a detailed x-ray diffraction structural study of Zr under pressure and unambiguously identify the existence of a first-order isostructural bcc-to-bcc phase transition near 58 GPa. First-principles quantum molecular dynamics lattice dynamics calculations support the existence of this phase transition, in excellent agreement with experimental results, triggered by anharmonic effects. Our results highlight the potential ubiquity of anharmonically driven isostructural transitions within the periodic table under pressure and calls for follow-up experimental and theoretical studies.

Compressibility and strength of nanocrystalline tungsten boride under compression to 60GPaStrength and elastic moduli of TiN from radial x-ray diffraction under nonhydrostatic compression up to 45 GPa Modeling of the elastic precursor behavior and dynamic inelasticity of tantalum under ramp wave loading to 17 GPa A magnetic loading technique was used to study the strength of polycrystalline tantalum ramp compressed to peak stresses between 60 and 250 GPa. Velocimetry was used to monitor the planar ramp compression and release of various tantalum samples. A wave profile analysis was then employed to determine the pressure-dependence of the average shear stress upon unloading at strain rates on the order of 10 5 s À1 . Experimental uncertainties were quantified using a Monte Carlo approach, where values of 5% in the estimated pressure and 9-17% in the shear stress were calculated. The measured deviatoric response was found to be in good agreement with existing lower pressure strength data as well as several strength models. Significant deviations between the experiments and models, however, were observed at higher pressures where shear stresses of up to 5 GPa were measured. Additionally, these data suggest a significant effect of the initial material processing on the high pressure strength. Heavily worked or sputtered samples were found to support up to a 30% higher shear stress upon release than an annealed material. V C 2014 AIP Publishing LLC.