Spectroscopy and Dynamics of Open-Shell van der Waals Molecules

在这个项目中的物理化学计划的化学 司，M.埃默里大学化学系天堂 将研究弱键相互作用和预解离动力学 开壳层货车范德华分子。 特别是货车德瓦耳斯 羟基、氰基和次甲基自由基与稀土形成的络合物， 将研究气体原子。 激发的电子态将是 其特征在于高分辨率荧光激发光谱， 荧光耗尽光谱和量子拍测量。 的 电子基态将由受激发射泵浦探测 技术. 对于较轻的系统，从头计算的 势能面将被执行，以补充 试验结果 电子和振动预离解将是 通过波长分辨荧光和脉冲激光研究 泵浦探测测量。 弱束缚货车德瓦耳斯复合体的研究是这一领域的前沿之一 当代物理化学领域。 虽然众多的货车范德瓦尔斯 由稳定的（闭合壳层）分子形成的复合物已经被 研究，这种复合物的研究，其中一个组成部分 成员是一个自由基（分子片段）仍处于早期阶段。 由于存在显着的电子自旋耦合的 自由基与其封闭的壳层伙伴，理论模型的发展， 封闭壳层货车德瓦耳斯络合物中的键相互作用不是 适用于开壳系统。 这项研究提供了重要的 开壳层货车德瓦耳斯配合物数据库 这些系统的理论模型。 这项研究的结果是， 与涉及开壳层的碰撞过程的工作直接相关 目前在几个实验室中进行的药物试验。

In this project in the Physical Chemistry Program of the Chemistry Division, Prof. M. Heaven of the Chemistry Department of Emory University will study the weak bonding interactions and predissociation dynamics of open shell van der Waals molecules. Specifically, the van der Waals complexes formed by the hydroxyl, cyanogen and methyne radicals with rare gas atoms will be investigated. The excited electronic states will be characterized by high resolution fluorescence excitation spectroscopy, fluorescence depletion spectroscopy, and quantum beat measurements. The electronic ground states will be probed by stimulated emission pumping techniques. For the lighter systems, ab initio calculations of the potential energy surfaces will be performed to complement the experimental results. Electronic and vibrational predissociation will be investigated through wavelength resolved fluorescence and pulsed laser pump-probe measurements. The study of weakly bound van der Waals complexes is one of the frontier areas of contemporary physical chemistry. While numerous van der Waals complexes formed by stable (closed shell) molecules have been investigated, the study of such complexes in which one of the component members is a radical (molecular fragment) is still in its early stages. Owing to the presence of significant electron spin couplings of the radical with its closed shell partner, theoretical models developed for the bonding interactions in closed shell van der Waals complexes are not applicable to open shell systems. This research provides an important data base for open shell van der Waals complexes for the development of theoretical models of these systems. The results of this research are of direct relevance to work on collisional processes involving open shell diatomics which is currently pursued in several laboratories.