Spectroscopy and Dynamics of Open-Shell Complexes

在这个由化学学部实验物理化学项目支持的项目中，Heaven将继续研究预反应范德华配合物H2-CN和CN-HCl的光谱和动力学。他将利用荧光激发和光-光双共振技术探测H2(D2)-CN(A)和-N(B)的反振动结构。特别是，他将研究A态络合物的预解离动力学。此外，Heaven将使用受激发射泵送（SEP）和受激拉曼激发（SRE）技术研究H2(D2)-CN(X)的振动激发水平。在与Morokuma和Bowman的合作中，Heaven提议从头计算CN-H2的基态和激发态的势能面。最后，他提出了CN-Rg和(N2+)-Rg （Rg= Ne或Ar）预解动力学的研究。弱束缚范德华配合物的研究是当代物理化学的前沿领域之一。虽然已经研究了许多由稳定（称为“闭壳”）分子形成的范德华配合物，但对其中一个组分是自由基（分子片段或“开壳”系统）的这种配合物的研究仍处于早期阶段。封闭壳层范德华配合物中键相互作用的理论模型不适用于开放壳层体系。本研究为研究开壳范德华配合物提供了重要的数据基础，有助于建立这些系统的理论模型。这项研究的结果与涉及开壳硅原子的碰撞过程的工作直接相关，目前在几个实验室进行，并在大气和工业过程中有应用。

In this project supported by the Experimental Physical Chemistry Program of the Chemistry Division, Heaven will continue his studies of the spectroscopy and dynamics of the pre-reactive van der Waals complexes H2-CN and CN-HCl. He will use fluorescence excitation and optical-optical double resonance techniques to probe the ro-vibronic structures of H2(D2)-CN(A) and -N(B). In particular, he will examine the predissociation dynamics of the A state complex. In addition, Heaven will investigate vibrationally excited levels of H2(D2)-CN(X) using stimulated emission pumping (SEP) and stimulated Raman excitation (SRE) techniques. In collaboration with Morokuma and Bowman, Heaven proposes to calculate ab initio potential energy surfaces for the ground and excited states of CN-H2. Finally, he proposes studies of the predissociation dynamics of CN-Rg and (N2+)-Rg (Rg= Ne or Ar). 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 (called `closed shell`) molecules have been investigated, the study of such complexes in which one of the component members is a radical (molecular fragment or `open shell` system) is still in its early stages. 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 that aids 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 and have applications in atmospheric and industrial processes.