State-to-State Photochemistry and Vibrational Spectroscopy of Molecular Complexes

米勒教授在实验物理化学计划的支持下，对各种中性二元、叔基和高阶分子络合物的动力学和光谱进行了实验研究。获得了关于这些络合物的结构以及振动激发的络合物的各种内部和平移(解离)自由度之间的能量流动的信息。光热探测技术被用来测量光碎片的角分布，并获得络合物中一个分子振动激发后的态到态光解离截面。这些结果深入了解了两个分离的光碎片分子之间的旋转态关联，并给出了络合解离能的精确值。计划的扩展将允许通过两个激光红外-红外双共振实验来探测这些络合物和稳定分子的更高振动状态。对于络合物，双共振技术还将允许实时测量预解离寿命。

Professor Miller is supported by the Experimental Physical Chemistry Program in experimental investigations on both the dynamics and spectroscopy of a variety of neutral binary, tertiary, and higher order molecular complexes. Information is obtained on the structures of these complexes and on the flow of energy between various internal and translational (dissociative) degrees of freedom for vibrationally-excited complexes. Opto-thermal detection techniques are used to measure photofragment angular distributions and obtain state-to-state photodissociation cross sections following vibrational excitation of one molecule in a complex. Results are yielding insight into rotational state correlations between two departing photofragment molecules and also give accurate values for the complex dissociation energies. Extensions are planned that will allow probing of higher vibrational states of both these complexes and stable molecules through a two laser IR-IR double resonance experiment. For the complexes, the double resonance technique will also allow measurements of predissociation lifetimes in real time.