The effects of water, formic acid, and nitric acid on N₂ and N₂O generation from NH₂NO and NH₂NO₂ are studied using high-level quantum-chemical calculations. It is shown that the reaction barriers from isolated NH₂NO and NH₂NO₂ are 35.5 and 38.1 kcal/mol, respectively. When the NH₂NO and NH₂NO₂ reactions are examined in the presence of water, formic acid, or nitric acid, the energy barriers are different. The mechanisms of these reactions are revealed through reaction pathway calculations. The isomerization of intermediate HNNOH and HNNOOH molecules, which follows a group rotation mechanism, plays a key role in reactions of isolated NH₂NO and NH₂NO₂. However, the presence of water, formic acid, or nitric acid changes the isomerization mechanism substantially. HNNOH or HNNOOH and the catalyzing molecule form a doubly hydrogen-bonded prereactive complex, which, in turn, facilities hydrogen atom migration (this is denoted as the hydrogen atom migration mechanism). This study demonstrates the feasibility of N₂ or N₂O generation from NH₂NO and NH₂NO₂ in the presence of water, formic acid, or nitric acid.

中文翻译：

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由NH2NO和NH2NO2生成酸促进N2和N2O生成的机理。

使用高级量子化学计算研究了水，甲酸和硝酸对NH ₂ NO和NH ₂ NO ₂生成N ₂和N ₂ O的影响。结果表明，分离出的NH ₂ NO和NH ₂ NO ₂的反应势垒分别为35.5 kcal / mol和38.1 kcal / mol。当NH ₂ NO和NH ₂ NO ₂在水，甲酸或硝酸的存在下检查反应，能量垒不同。这些反应的机理通过反应途径的计算得以揭示。遵循基团旋转机制的中间HNNOH和HNNOOH分子的异构化在分离的NH ₂ NO和NH ₂ NO _2的反应中起关键作用。然而，水，甲酸或硝酸的存在大大改变了异构化机理。HNNOH或HNNOOH与催化分子形成双氢键预反应络合物，进而促进氢原子迁移（这称为氢原子迁移机理）。这项研究证明了N ₂或N的可行性₂选自NH阿代₂ NO和NH ₂ NO ₂中的水，甲酸，或硝酸的存在。