Photoinitiated Reactions in Weakly Bonded Complexes

实验物理化学计划继续支持Wittig教授对弱结合气相复合体中的光引发反应的开创性研究。一个脱离光解离分子的氢原子，在初始条件下与相邻的弱成键分子发生反应，比通常的动力学过程研究中的情况要精确得多。关于反应过程的详细动力学，有可能获得重要的见解。对于暂时被困在另一个光解离碎片和最初的范德华键伙伴之间的轻氢原子，Wittig正在寻找作为初始光解条件的函数的可能的动力学共振。其他工作使用速度对准的多普勒光谱技术来完整地表征氢原子与一氧化二氮反应的产物激发，包括产物内态之间的关联。还将进行扩展，以允许研究涉及与分子弱键合的自由基的络合物。各种络合物的结构正在通过辅助的高分辨率可调谐半导体激光光谱测量来确定。

The Experimental Physical Chemistry Program is continuing support of Professor Wittig in pioneering investigations of photoinitiated reactions within weakly-bonded gas-phase complexes. A hydrogen atom, departing a photodissociated molecule, reacts with the neighboring weakly-bonded molecule under initial conditions much more precisely defined than is the case in typical investigations of kinetic processes. Significant insight is potentially available concerning the detailed dynamics of the reaction process. For the light hydrogen atom momentarily trapped between the other photodissociation fragment and an initially van der Waals-bonded partner, Wittig is searching for possible dynamical resonances as a function of the initial photodissociation conditions. Other work uses the velocity aligned Doppler spectroscopy technique to characterize completely the product excitations, including correlations between product internal states, for hydrogen atom reactions with nitrous oxide. Extensions will also be made to allow the investigation of complexes involving radicals weakly bonded to molecules. Structures of the various complexes are being determined with supplementary high-resolution tunable diode laser spectroscopy measurements.