Publications

This report summarizes the work performed as part of a one-year LDRD project, 'Evolutionary Complexity for Protection of Critical Assets.' A brief introduction is given to the topics of genetic algorithms and genetic programming, followed by a discussion of relevant results obtained during the project's research, and finally the conclusions drawn from those results. The focus is on using genetic programming to evolve solutions for relatively simple algebraic equations as a prototype application for evolving complexity in computer codes. The results were obtained using the lil-gp genetic program, a C code for evolving solutions to user-defined problems and functions. These results suggest that genetic programs are not well-suited to evolving complexity for critical asset protection because they cannot efficiently evolve solutions to complex problems, and introduce unacceptable performance penalties into solutions for simple ones.

Confinement within the nanoscale pores of a zeolite strongly modifies the behavior of small molecules. Typical of many such interesting and important problems, realistic modeling of this phenomena requires simultaneously capturing the detailed behavior of chemical bonds and the possibility of collective dynamics occurring in a complex unit cell (672 atoms in the case of Zeolite-4A). Classical simulations alone cannot reliably model the breaking and formation of chemical bonds, while quantum methods alone are incapable of treating the extended length and time scales characteristic of complex dynamics. We have developed a robust and efficient model in which a small region treated with the Kohn-Sham density functional theory is embedded within a larger system represented with classical potentials. This model has been applied in concert with first-principles electronic structure calculations and classical molecular dynamics and Monte Carlo simulations to study the behavior of water, ammonia, the hydroxide ion, and the ammonium ion in Zeolite-4a. Understanding this behavior is important to the predictive modeling of the aging of Zeolite-based desiccants. In particular, we have studied the absorption of these molecules, interactions between water and the ammonium ion, and reactions between the hydroxide ion and the zeolite cage. We have shown that interactions with the extended Zeolite cage strongly modifies these local chemical phenomena, and thereby we have proven out hypothesis that capturing both local chemistry and collective phenomena is essential to realistic modeling of this system. Based on our results, we have been able to identify two possible mechanisms for the aging of Zeolite-based desiccants.

Abstract not provided.

We have developed force fields for the calculation of adsorption of NH{sub 3}, CO{sub 2}, and H{sub 2}O on zeolite 4A by performing Gibbs ensemble Monte Carlo simulations to fit experimental isotherms at 298 K. The calculated NH{sub 3} and CO{sub 2} isotherms are in excellent agreement with experimental data over a wide range of temperatures and several orders of magnitude in pressure. We have calculated isotherms for H{sub 2}O in 4A using two different models and have found that H{sub 2}O saturates zeolite 4A even at pressures as low as 0.01 kPa for the range of temperatures studied. We have studied the geometry of the adsorption sites and their dependence on loading. At low pressures, CO{sub 2} molecules adsorb with their longitudinal axis pointing toward the center of the supercage, whereas at higher pressures, the two oxygen atoms are equidistant from the Na atom in the binding site.

There is currently a great need for solid state lasers that emit in the infrared. Whether or not conjugated polymers that emit in the IR can be synthesized is an interesting theoretical challenge. We show that emission in the IR can be achieved in designer polymers in which the effective Coulomb correlation is smaller than that in existing systems. We also show that the structural requirement for having small effective Coulomb correlations is that there exist transverse {pi}--conjugation over a few bonds in addition to longitudinal conjugation with large conjugation lengths.

Abstract not provided.

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The authors present the results of molecular dynamics simulations of n-butane and isobutane in silicalite. They begin with a comparison of the bulk adsorption and diffusion properties for two different parameterizations of the interaction potential between the hydrocarbon species, both of which have been shown to reproduce experimental gas-liquid coexistence curves. They examine diffusion as a function of the loading of the zeolite, as well as the temperature dependence of the diffusion constant at loading and for infinite dilution. They continue with simulations in which interfaces are formed between single component gases and the zeolite. After reaching equilibrium, they examine the dynamics of exchange between the bulk gas and the zeolite. Finally, they calculate the permeability of the zeolite for n-butane and isobutane as a function of pressure. Their simulations are performed for a number of different gas temperatures and pressures, covering a wide range of state points.