Defense Date


Document Type


Degree Name

Doctor of Philosophy



First Advisor

Dr. Shiv N. Khanna


Calculations have been carried out to investigate the stability and electronic structure of aluminum iodide clusters using first principles gradient-corrected density functional theory. Analysis of A113Ix-, A114Ix-, and A17I- clusters reveals that their stability is governed by the geometrically unperturbed A113-, A1142+, and A17+ units, respectively, that are demonstrated to constitute the compact cores of the clusters upon significant iodine content. The compact, icosahedral A113, icosahedral-like A1 14, and capped square bi-pyramid A17 superatom structures of the stable aluminum cores have an analogous electronic configuration to that of halogen, alkaline-earth, and alkaline atoms, respectively. Novel chemistry is demonstrated in superatoms, arising from two primary sources. Firstly, the calculations demonstrate the preference to break molecular I2 bonds in favor of iodine atoms individually adsorbing onto the aluminum sites of the central aluminum core surface. Secondly, the calculation show that observations of alternating stability trends dependent on the number of iodine ligands are connected to the formation and quenching of active sites. The significance of the induced active centers on aluminum iodide clusters upon association to alkenes is addressed, demonstrating a method towards predicting the location and extent of binding hydrocarbons. The novel chemistry of superatoms allows for a host of possible applications that integrate their unique properties in original ways and some key examples are described. Superatoms are the analogs to atoms and subsequently, just as the periodic table of elements lists atoms that can assemble into molecules and lattice structures, there exists the fathomable possibility to incorporate superatoms into extended structures such that they maintain their unique properties and result in a new class of materials. Initiation of such cluster-materials insinuates that cluster-mediated periodic table may be a proper extension to allow for a simple means for conveying fundamental information about clusters.


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Is Part Of

VCU Theses and Dissertations

Date of Submission

June 2008

Included in

Chemistry Commons