Selective Evolution of Chemical Reactions on Excited Electronic Potential Energy Surfaces

有了实验物理化学的资助，巴特勒博士将 开展一系列研究，重点调查 非绝热相互作用主导了化学物质的演化， 激发态电子势能面上的反应。 工作 将利用偏振发射光谱，测量 在分子过程中发射的光子的波长和偏振 解离，结合状态选择性激光激发， 产品检测技术。 这些研究旨在阐明 能量上允许的分解通道之间的分支 可以对电子表面的性质非常敏感 以及随后的分子内能量转移过程 以及与其它电子表面的非绝热相互作用， 清白的. 这项工作的重要性在于有可能控制 通过光激发化学反应的产物， 电子国。 许多实例包括以下的光诱导反应： 吸附在表面上的分子，碰撞中的能量转移， 电子激发或开壳原子或分子，和 在气相或溶液中的双分子或单分子反应。 当这项工作探索分子结构和动力学因素时， 允许光诱导选择性化学反应， 在热激发时发生，结果可以促进 发展合成化学的新方法。

With this grant in Experimental Physical Chemistry, Dr. Butler will initiate a series of studies which focus on investigating the nonadiabatic interactions which dominate the evolution of chemical reactions on excited electronic potential energy surfaces. The work will utilize polarized emission spectroscopy, which measures the wavelength and polarization of photons emitted during molecular dissociation, in conjunction with state-selective laser excitation and product detection techniques. The studies are designed to elucidate how the branching between energetically allowed decomposition channels can be critically sensitive to the nature of the electronic surface accessed, and the subsequent intramolecular energy transfer processes and nonadiabatic interactions with other electroinc surfaces during dissociation. The significance of the work lies in the potential for controlling the products of chemical reactions via photoexcitation to particular electronic states. Numerous examples include photoinduced reactions of molecules adsorbed on surfaces, energy transfer in collisions of electronically excited or open shell atoms or molecules, and bimolecular or unimolecular reaction in the gas phase or in solution. As the work explores what molecular structural and dynamical factors allow one to photoinduce a selective chemical reaction which would not occur upon thermal excitation, the results could advance the development of new methods of synthetic chemistry.