Unimolecular Reaction Dynamics

摩尔在实验物理化学项目的支持下，继续研究分子基电子状态下化学键断裂的动力学，目标是为热反应和状态选择的单分子反应开发定量预测模型。将对甲酰基氟进行光谱和动力学测量，其中分子内振动能量再分配和HF + CO的解离过程以相当的速率进行，并且观察到的速率常数强烈依赖于旋转和振动量子数。初态和末态可以用实验完全解出。测量结果将与定量的、最先进的动力学模型进行详细的比较。这些结果将有助于确定过渡态理论的有效性限制，并揭示状态选择化学的可能性。需要对基准分子系统的化学反应进行全面详细的了解，为开发复杂实际系统的定量预测模型奠定基础。这项研究的结果将为模拟燃烧和大气过程中涉及的化学过程提供有用的见解。

Moore is supported by the Experimental Physical Chemistry Program to continue his studies of the dynamics of chemical bond breaking in the ground electronic states of molecules, with the goal to develop quantitatively predictive models for both thermal and state-selected unimolecular reactions. A combination of spectroscopic and dynamical measurements will be performed on formyl fluoride, where intramolecular vibrational energy redistribution and the dissociation process to HF + CO proceed at comparable rates, and observed rate constants depend strongly on rotational and vibrational quantum number. Initial and final states may be fully resolved experimentally. The measurements will be compared in detail with quantitative, state-of-the-art dynamical models. These results will then help set the limits of validity for transition state theories, and reveal the possibilities for state-selective chemistry. Full detailed understanding of chemical reactions for benchmark molecular systems is needed to lay the groundwork for developing quantitatively predictive models for complex practical systems. Outcomes from this research will yield insights useful for modeling the chemistry involved in combustion and atmospheric processes.