Structure Determinations of Methyl- and Fluoromethyl Nitrate XCH2ONO2 (X = H, F) in the Solid and Gaseous Phases

本文拟对硝酸甲酯（H3CONO2）和硝酸氟甲基（FH2CONO2）在固相和气相下的结构进行实验研究。硝酸甲酯是有机硝酸盐的母体分子，因此具有重要意义。对于硝酸氟甲基，我们的目的是了解与电负性极强的氟基取代的作用。结构数据将有助于了解这些高能材料的不同行为和不同灵敏度。迄今为止，只有对硝酸甲基的微波光谱研究，但这两种化合物没有其他结构数据。我们计划通过对这些液体物质应用合适的结晶技术来阐明它们的晶体结构，以便获得用于x射线衍射的晶体，从而导致固态的可分解结构。我们还计划通过电子衍射实验和衍射数据分析来探索实验气相，也可以通过衍射数据和旋转常数的联合分析，必要时还可以使用复杂的分子动力学描述。样品制备的优化将在慕尼黑进行，但结构化学研究的样品必须由来自比勒费尔德慕尼黑实验室的经验丰富的人员制备，因为这两种化合物对冲击和摩擦都很敏感，并且是爆炸物。结构化学实验将在比勒菲尔德的核心设施GED@BI（气体电子衍射和小分子结构中心）进行，并将伴随着高水平的量子化学方法。

We propose to study the structures of methyl nitrate (H3CONO2) and fluoromethyl nitrate (FH2CONO2) experimentally in the solid state and the gas phase. Methyl nitrate is the parent molecule for organic nitrates and thus of fundamental interest. With fluoromethyl nitrate we aim at understanding the role of substitution with the extremely electronegative fluorine group. The structural data will serve to understand the different behaviour and the different sensitivity of these highly energetic materials. There is so far only a microwave spectroscopy study on methyl nitrate, but otherwise there are no structural data available for these two compounds. We plan to elucidate their crystal structures by applying suitable crystallization techniques to these liquid substances in order to gain crystals for X-ray diffraction that lead to resolvable structures of the solid state. We also plan to explore the experimental gas phase by electron diffraction experiments and analysis of the diffraction data – also by joint analysis of diffraction data and rotational constants, and if necessary with sophisticated dynamic descriptions of the molecules. The optimisation of the sample preparation will be performed in Munich, but the samples for structural chemistry studies have to be prepared by an experienced person from the Munich labs in Bielefeld, as both compounds are sensitive to shock and friction and are explosives. The structural chemistry experiments will be carried out in the core facility GED@BI (Centre of Gas Electron Diffraction and Small Molecule Structures) in Bielefeld and will be accompanied by high level quantum-chemical methods.