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

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Ionothermal synthesis, the use of ionic liquids as both solvent and template (structure-directing agent), has been used to prepare zeolites and inorganic-organic hybrids such as metal-organic frameworks. The underlying properties of the ionothermal method are discussed, and it is compared with traditional hydrothermal preparative methods. The materials resulting from ionothermal synthesis are described, and any structural features that can be related to the ionic liquid used as the solvent are discussed. Future areas of potential interest are also considered.

Ionothermal synthesis of zeolites, metal-organic frameworks, and inorganic-organic hybrids.

The increasing amount of papers published on ionic liquids generates an extensive quantity of data. The thermal stability data of divergent ionic liquids are collected in this paper with attention to the experimental set-up. The influence and importance of the latter parameters are broadly addressed. Both ramped temperature and isothermal thermogravimetric analysis are discussed, along with state-of-the-art methods, such as TGA-MS and pyrolysis-GC. The strengths and weaknesses of the different methodologies known to date demonstrate that analysis methods should be in line with the application. The combination of data from advanced analysis methods allows us to obtain in-depth information on the degradation processes. Aided with computational methods, the kinetics and thermodynamics of thermal degradation are revealed piece by piece. The better understanding of the behaviour of ionic liquids at high temperature allows selective and application driven design, as well as mathematical prediction for engineering purposes.

Ionic liquid thermal stabilities: decomposition mechanisms and analysis tools

Chapter 22 – inverse radiative heat transfer

Confined rapid thermolysis/FTIR/ToF studies of imidazolium-based ionic liquids

Thermal decomposition studies of energetic materials using confined rapid thermolysis / FTIR spectroscopy

During the combustion of solid propellants, explosives, or pyrotechnics, the condensed phase experiences heating rates that may exceed 20,000 K/s. At such high heating rates, the thermal decomposition behavior of the energetic material could be affected by its rate of decomposition. To simulate the high heating rate environment, the T-jump experiment was developed for use with Fourier-transform infrared spectroscopy. The T-jump experiment utilizes electrical resistance heating of a thin Pt filament on which a small amount of the energetic test sample is placed. This work describes a heat transfer model of the filament and sample, a model of the current's control circuit, and global decomposition and heat release mechanisms of Cyclotrimethylenetrinitramine (RDX), which is an energetic ingredient .used in propellants and explosives. Comparisons of model calculations with experimental data reveal an excellent agreement. Similarly, the predicted time to rapid heat release for the highly energetic RDX sample also shows a good agreement with experimental results. Thus the use of the developed model in conjunction with experiments should be a useful tool in studying the thermal decomposition behavior of energetic materials under combustion-like conditions.

Stefan T. Thynell

Papers

Confined rapid thermolysis/FTIR/ToF studies of imidazolium-based ionic liquids

Thermal decomposition studies of energetic materials using confined rapid thermolysis / FTIR spectroscopy

Condensed-phase kinetics of cyclotrimethylenetrinitramine by modeling the T-jump/infrared spectroscopy experiment

Effect of anisotropic thermal conductivity of the GDL and current collector rib width on two-phase transport in a PEM fuel cell

Discrete-ordinates method in radiative heat transfer