Theoretical Studies of Organosilicon and Main Group Organometallic Chemistry

在物理化学计划的支持下，首席研究员将对主族有机金属化学进行全面的理论研究，重点是硅及其在元素周期表中的其他元素。对这些元素的电子结构和化学键的透彻理解具有重要的基础和实际意义。这些元素构成了工业上重要的聚合物（如硅树脂）的骨干，也是电子芯片的基本基板。将使用最先进的电子结构理论，结合量子和半经典动力学研究来预测反应动力学和机制。研究领域包括分析基本反应机理，如氢化反应、偶联反应和重排反应。其他需要考虑的反应类型包括含硅化合物与原子氧和分子氧之间的反应、化学气相沉积中的重要反应、硅中心的SN2反应、五配位反应中间体中假旋合的作用、硅烷的单分子分解、二价IV基团的反应、以及小的阳离子和阴离子的反应。高应变环的分子和电子结构、性质和反应性也将被研究，以及各种不同寻常的键排列的性质。将对含有主族金属和小簇主族金属的生物活性化合物进行结构和反应性的初步调查。理论研究将包括发展第四和第五周期元素的扩展基集，继续探索连接电子结构和动力学计算的技术，以及开发从头计算和半经验计算的连接方法。

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.