Thermal decomposition of hydrazines from reactive dynamics using the ReaxFF reactive force field

We report reactive dynamics (RD) studies on: the decomposition of bulk hydrazine (N(2)H(4)); the decomposition of bulk monomethyl-hydrazine (CH(3)N(2)H(3)), hereafter referred to simply as methyl-hydrazine; the decomposition of hydrazine in the presence of hydrogen peroxide (H(2)O(2)); and decomposition hydrazine on catalytic surfaces Pt[100] and Pt[111] under various conditions. These studies use the ReaxFF reactive force field to describe the multitude of chemical reactions in these systems for a variety of reaction conditions in order to show that this approach leads to realistic decomposition mechanisms and rates. In particular, we determined how the decomposition of hydrazine is affected by temperature, pressure, and heating rate. We analyzed chemical reaction mechanism of the decomposition of hydrazine at the studied conditions and found that at lower temperatures the initial product from hydrazine decomposition is NH(3), whereas at higher temperatures H(2) and N(2) are the dominant early products. Prominent intermediates observed during these decompositions include N(2)H(3), N(2)H(2,) and NH(2), in agreement with quantum mechanical studies (7.3 ps at 3000 K). As the heating rate is decreased, the onset for hydrazine decomposition shifts to lower temperatures. Using a constant heating rate, we found that higher pressure (increased density) favors formation of NH(3) over N(2) and H(2). In studies of the catalytic decomposition of hydrazine on surfaces Pt[100] and Pt[111], we found that the presence of a Pt-catalyst reduces the initial decomposition temperature of hydrazine by about 50%. We found that the Pt[100]-surface is 20 times more active for hydrazine decomposition than the Pt[111]-surface, in qualitative agreement with experiments. These studies indicate how ReaxFF RD can be useful in understanding the chemical processes involved in bulk and catalytic decomposition and in oxidation of reactive species under various reaction conditions.