MOLECULAR DYNAMICS STUDIES OF SIMPLE MODEL FLUIDS AND WATER CONFINED IN CARBON NANOTUBE

Molecular Dynamics (MD) simulation is one of the most important computational techniques with broad applications in physics, chemistry, chemical engineering, materials design and biological science. Traditional computational chemistry refers to quantum calculations based on solving Schrodinger equations. Later developed Density Functional Theory (DFT) based on solving Kohn-Sham equations became the more popular ab initio calculation technique which could deal with ~1000 atoms by explicitly considering electron interactions. In contrast, MD simulation based on solving classical mechanics equations of motion is a totally different technique in the field of computational chemistry. Electron interactions were implicitly included in the empirical atom-based potential functions and the system size to be investigated can be extended to ~106 atoms. The thermodynamic properties of model fluids are mainly determined by macroscopic quantities, like temperature, pressure, density. The quantum effects on thermodynamic properties like melting point, surface tension are not dominant. In this work, we mainly investigated the melting point, surface tension (liquid-vapor and liquid-solid) of model fluids including Lennard-Jones model, Stockmayer model and a couple of water models (TIP4P/Ew, TIP5P/Ew) by means of MD simulation. In addition, some new structures of water confined in carbon nanotube were discovered and transport behaviors of water and ions through nano-channels were also revealed.

Structural and Magnetic Properties of Neodymium - Iron - Boron Clusters

Using inert gas condensation techniques the properties of sputtered neodymium-iron-born clusters were investigated. A D.C. magnetron sputtering source created vaporous Nd-Fe-B which was then condensed into clusters and deposited onto silicon substrates. A composite target of Nd-Fe-B discs on an iron plate and a composite target of Nd-(Fe-Co)-B were utilized to create clusters. The clusters were coated with a carbon layer through R.F. sputtering to prevent oxidation. Samples were investigated in the TEM and showed a size distribution with an average particle diameter of 8.11 nm. The clusters, upon deposition, were amorphous as indicated by diffuse diffraction patterns obtained through SAD. The EDS showed compositionally a direct correlation in the ratio of rare-earth to transition metals between the target and deposited samples. The magnetic properties of the as-deposited clusters showed superparamagnetic properties at high temperatures and ferromagnetic properties at low temperatures; these properties are indicative of rare-earth transition metal amorphous clusters. Annealing of samples showed an initial increase in the coercivity. Samples were annealed in an inert gas atmosphere at 600o C for increasing amounts of time. The samples showed an initial increase in coercivity, but showed no additional increases with additional annealing time. SAD of annealed cluster samples showed the presence of Nd2Fe17 and a bcc-Nd phase. The bcc-Nd is the result of oxidation at high temperatures created during annealing and surface interface energy. The magnetic properties of the annealed samples showed weak coercivity and a saturation magnetization equivalent to that of Nd2Fe17. The annealed clusters showed a slight increase in coercivity at low temperatures. These results indicate a loss of boron during the sputtering process.

Theoretical and Experimental Studies in Nuclear Magnetic Resonance

Nuclear magnetic resonance (NMR) is a tool used to probe the physical and chemical environments of specific atoms in molecules. This research explored small molecule analogues to biological materials to determine NMR parameters using ab initio computations, comparing the results with solid-state NMR measurements. Models, such as dimethyl phosphate (DMP) for oligonucleotides or CuCl for the active site of the protein azurin, represented computationally unwieldy macromolecules. 31P chemical shielding tensors were calculated for DMP as a function of torsion angles, as well as for the phosphate salts, ammonium dihydrogen phosphate (ADHP), diammonium hydrogen phosphate, and magnesium dihydrogen phosphate. The computational DMP work indicated a problem with the current standard 31P reference of 85% H3PO4(aq.). Comparison of the calculations and experimental spectra for the phosphate salts indicated ADHP might be a preferable alternative as a solid state NMR reference for 31P. Experimental work included magic angle spinning experiments on powder samples using the UNL chemistry department’s Bruker Avance 600 MHz NMR to collect data to determine chemical shielding anisotropies. For the quadrupolar nuclei of copper and scandium, the electric field gradient was calculated in diatomic univalent metal halides, allowing determination of the minimal level of theory necessary to compute NMR parameters for these nuclei.

THE ROLE OF INDUSTRY IN DEVELOPING NEW MATERIALS FOR VERTEBRATE PEST CONTROL

In the first paper presented to you today by Dr. Spencer, an expert in the Animal Biology field and an official authority at the same time, you heard about the requirements imposed on a chemical in order to pass the different official hurdles before it ever will be accepted as a proven tool in wildlife management. Many characteristics have to be known and highly sophisticated tests have to be run. In many instances the governmental agency maintains its own screening, testing or analytical programs according to standard procedures. It would be impossible, however, for economic and time reasons to work out all the data necessary for themselves. They, therefore, depend largely on the information furnished by the individual industry which naturally has to be established as conscientiously as possible. This, among other things, Dr. Spencer has made very clear; and this is also what makes quite a few headaches for the individual industry, but I am certainly not speaking only for myself in saying that Industry fully realizes this important role in developing materials for vertebrate control and the responsibilities lying in this. This type of work - better to say cooperative work with the official institutions - is, however, only one part and for the most of it, the smallest part of work which Industry pays to the development of compounds for pest control. It actually refers only to those very few compounds which are known to be effective. But how to get to know about their properties in the first place? How does Industry make the selection from the many thousands of compounds synthesized each year? This, by far, creates the biggest problems, at least from the scientific and technical standpoint. Let us rest here for a short while and think about the possible ways of screening and selecting effective compounds. Basically there are two different ways. One is the empirical way of screening as big a number of compounds as possible under the supposition that with the number of incidences the chances for a "hit" increase, too. You can also call this type of approach the statistical or the analytical one, the mass screening of new, mostly unknown candidate materials. This type of testing can only be performed by a producer of many new materials,that means by big industries. It requires a tremendous investment in personnel, time and equipment and is based on highly simplified but indicative test methods, the results of which would have to be reliable and representative for practical purposes. The other extreme is the intellectual way of theorizing effective chemical configurations. Defenders of this method claim to now or later be able to predict biological effectiveness on the basis of the chemical structure or certain groups in it. Certain pre-experience should be necessary, that means knowledge of the importance of certain molecular requirements, then the detection of new and effective complete molecules is a matter of coordination to be performed by smart people or computers. You can also call this method the synthetical or coordinative method.