Untangling the Energetics and Dynamics of Reactions of Ground State Silicon Atoms with Small Hydrocarbon Radicals

在这项由化学系化学结构、动力学和机制计划资助的奖项中，夏威夷大学马诺阿分校的Kaiser教授和他的研究生们将解开与有机硅小分子形成有关的能量学、动力学和势能面(PESS)。为了实现这些目标，Kaiser教授和他的同事们将在无烃交叉分子束机器中研究基态硅原子与小碳氢自由基在单一碰撞条件下的能量相关化学反应动力学。这一装置结合了一个通用的、可旋转的角分辨飞行时间质谱计检测器，具有硬电子和软电子碰撞电离以及激光诱导荧光(LIF)检测。通过进行这些交叉分子束实验，并将结果与从头计算和准经典轨迹(QCT)计算相结合，可以提取有机硅小分子的化学动力学、反应机理、产物、中间体、能量学、支化比和生成热。除了揭开迄今探索得很少的原子-自由基反应的化学动力学的目标外，拟议的研究可能会影响其他领域，通过更好地理解星际介质中有机硅小分子的形成和作用(天体化学)；在化学气相沉积过程中(材料科学)；以及对主要组元素的化学键(物理有机化学)提供新的见解。研究和教育的一体化将通过与高中教师的接触和让本科生参与反应动力学和天体化学的实践活动来实现。来自当地夏威夷人等代表性不足群体的学生将被特别鼓励参加。此外，国际天体化学协会还将在2010年檀香山太平洋会议上组织一次关于天体化学的跨学科会议。

In this award, funded by the Chemical Structure, Dynamics and Mechanisms Program of the Division of Chemistry, Professor Kaiser of the University of Hawaii at Manoa and his graduate students will untangle the energetics, dynamics, and potential energy surfaces (PESs) involved in the formation of small organo silicon molecules. To achieve these goals, Professor Kaiser and his colleagues will investigate the energy-dependent chemical reaction dynamics of ground state silicon atoms with small hydrocarbon radicals under single collision conditions in a hydrocarbon-free, crossed molecular beam machine. This setup incorporates a universal, rotatable angular resolved time-of-flight mass spectrometric detector with hard and soft electron impact ionization as well as laser induced fluorescence (LIF) detection. By conducting these crossed molecular beam experiments and combining the results with ab initio and quasi classical trajectory (QCT) calculations in collaboration with Professor Head-Gordon (UC Berkeley), the chemical dynamics, reaction mechanisms, products, intermediates, energetics, branching ratios, and enthalpies of formation of small organo silicon molecules can be extracted. Aside from the goal of unraveling the chemical dynamics of hitherto poorly explored atom-radical reactions, the proposed studies may impact other areas through an improved understanding of the formation and role of small organo silicon molecules in the interstellar medium (astrochemistry); in chemical vapor deposition processes (material sciences); and in providing new insights into chemical bonding of main group elements (physical organic chemistry).Integration of research and education will be achieved by outreach to high school teachers and involving undergraduate students in hands-on activities in reaction dynamics and astrochemistry. Students from underrepresented groups such as local Hawai'ians will be particularly encouraged to participate. In addition, the PI will organize an interdisciplinary session on astrochemistry at the Pacifichem 2010 in Honolulu.