Spectroscopy and Dynamics of Open-Shell Complexes

开壳配合物的光谱学和动力学

• 批准号: 9810106
• 负责人: Michael Heaven
• 金额: $ 36.55万
• 依托单位: Emory University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1998
• 资助国家: 美国
• 起止时间: 1998-09-01 至 2002-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9810106&HistoricalAwards=false
• 关键词: Spectroscopy; Dynamics; Open; Shell; Complexes

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.

在这个由化学部实验物理化学计划支持的项目中，天堂将继续他对反应前范德华络合物H2-CN和CN-HCl的光谱和动力学的研究。他将使用荧光激发和光学-光学双共振技术来探测H2(D2)-CN(A)和-N(B)的振动结构。特别是，他将研究A态复合体的预解离动力学。此外，Heaven将使用受激发射泵浦(SEP)和受激拉曼激发(SRE)技术研究H2(D2)-CN(X)的振动激发能级。在与Morokuma和Bowman的合作中，Heaven提议计算CN-H2的基态和激发态的从头算势能面。最后，他建议研究CN-Rg和(N~2+)-Rg(Rg=Ne或Ar)的预解离动力学。弱结合范德华络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的(称为‘闭壳层’)分子形成的范德华络合物，但对于其中一个成员是自由基(分子碎片或‘开壳层’体系)的此类络合物的研究仍处于早期阶段。为闭合壳层范德华络合物中的键相互作用建立的理论模型不适用于开壳体系。这一研究为研究开壳范德华络合物提供了重要的数据基础，有助于这些体系的理论模型的发展。这项研究的结果与涉及开壳硅藻的碰撞过程的工作直接相关，该过程目前正在几个实验室进行，并在大气和工业过程中得到应用。