Theoretical Studies of Organosilicon and Main Group Organometallic Chemistry

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With the support of the Physical Chemistry Program the Principal Investigator will undertake a comprehensive theoretical study of main group organometallic chemistry, with an emphasis on silicon and the other elements in its group in the periodic table. A thorough understanding of the electronic structures and chemical bonding of these elements is of both fundamental and practical importance. These elements constitute the backbones of industrially important polymers, such as the silicones, and are the basic substrates of electronic chips. State-of-the-art electronic structure theory, interfaced with quantum and semi-classical dynamics studies for the prediction of reaction dynamics and mechanisms, will be used. Areas to be investigated include analysis of fundamental reaction mechanisms, such as the hydrosilation, coupling and rearrangement reactions. Other reaction types to be considered include those between silicon-containing compounds and atomic and molecular oxygen, reactions of importance in chemical vapor deposition, SN2 reactions at silicon centers, and the role of pseudorotation in the pentacoordinated reactive intermediates, unimolecular decompositions of silanes, reactions of divalent group IV species, and reactions of small cations and anions. The molecular and electronic structures, properties and reactivity of highly strained rings will be investigated also, as will the nature of a variety of unusual bonding arrangements. Initial investigations of structure and reactivity will be undertaken for biologically active compounds which contain main group metals and small clusters of main group metals. Theoretical investigations will include the development of extended basis sets for fourth and fifth period elements, continued explorations of techniques for interfacing electronic structure and dynamics calculations, and the development of methods for interfacing ab initio and semi- empirical calculations.