Unimolecular Reaction Dynamics

摩尔是由实验物理化学计划的支持，继续他的研究化学键断裂的分子的基态电子态的动力学，目标是开发定量预测模型的热和状态选择单分子反应。 光谱和动力学测量的组合将进行甲酰氟，分子内振动能量的重新分配和HF + CO的解离过程进行在可比的速率，和观察到的速率常数强烈依赖于旋转和振动量子数。 初始状态和最终状态可以通过实验完全分辨。 测量结果将与定量的、最先进的动力学模型进行详细比较。这些结果将有助于确定过渡态理论的有效性极限，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充分详细的了解，以便为复杂的实际系统开发定量预测模型奠定基础。 这项研究的结果将产生有用的见解，用于模拟燃烧和大气过程中所涉及的化学。

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.