Theoretical Studies of Organosilicon and Main Group Organometallic Chemistry

在物理化学计划的支持下， 首席研究员将进行全面的 主族有机金属化学的理论研究， 强调硅及其族中的其他元素， 元素周期表全面了解电子 这些元素的结构和化学键合都是 具有根本性和现实意义。这些元件构成 工业上重要的聚合物的主链，例如 硅树脂，并且是电子芯片的基本衬底。 最先进的电子结构理论， 预测的量子和半经典动力学研究 反应动力学和机制，将被使用。领域得到 研究包括基本反应分析 机制，如硅氢化、偶联和 重排反应需要考虑的其他反应类型 包括含硅化合物和原子之间那些 和分子氧，化学气相中重要的反应 沉积，在硅中心的SN2反应，以及 五配位反应性中间体中的假旋转， 硅烷的单分子分解，二价硅烷的反应， IV族物种，以及小阳离子和阴离子的反应。 分子和电子结构，性质和 还将研究高应变环的反应性， 以及各种不寻常的结合的性质 安排初步调查的结构和 将对生物活性化合物进行反应 其含有主族金属和小的主族金属簇， 金属族。理论研究将包括 为第四和第五期拟订扩展的成套基准 元素，继续探索技术， 电子结构和动力学计算， 从头算和半从头算接口方法的开发 经验计算

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.