Ab initio search for novel borohydride building blocks with potential for hydrogen storage.

摘要

On-board hydrogen storage presents a challenging barrier to the use of hydrogen as an energy source because the performance of current storage materials falls short of platform requirements. Because boron is one of the lightest chemical elements that can form strong covalent bonds with hydrogen, it provides an excellent opportunity to design new lightweight materials on the basis of novel boron hydride building blocks. Realizing this potential requires an understanding of the electronic structure, chemical bonding, and stability of neutral and anionic BxHy clusters with variable stoichiometry. While a large number of boron hydride compounds are known, there are still entire classes of yet unknown neutral and anionic BxHy clusters and molecules with various new x/y ratios which may be good candidates for hydrogen storage or as intermediates of borane dehydrogenation. The primary aim of this dissertation was to search for neutral and anionic BxHy clusters that are thermochemically stable towards hydrogen release and to understand the chemical bonding in these novel clusters. These goals were accomplished by performing an unbiased search for neutral and anionic global minimum B xHy clusters using ab initio methods.;In addition to finding a rich variety of new neutral and anionic B xHy (x = 3 -- 6 and y = 4 -- 7) clusters that could be building blocks for novel hydrogen-boron materials during the course of conducting this research, optical isomerism was discovered in select neutral and anionic boron-hydride clusters. Furthermore, the transition from planar to 3-dimensional geometries in global minimum B 6Hx- clusters was discovered using ab initio techniques during this study. Chemical bonding analysis using the AdNDP method was performed for all global minimum structures and low-lying isomers. The chemical bonding pattern recovered by the AdNDP method in all cases is consistent with the geometric structure. The theoretical vertical detachment energies presented in this dissertation may help interpret future photoelectron spectroscopic studies of the anions presented here.