Han Yulun, Hobbie Erik K, Kilin Dmitri S
Department of Chemistry and Biochemistry , North Dakota State University , Fargo , North Dakota 58102 , United States.
Department of Physics , North Dakota State University , Fargo , North Dakota 58102 , United States.
J Phys Chem Lett. 2019 May 16;10(10):2394-2399. doi: 10.1021/acs.jpclett.9b00674. Epub 2019 Apr 30.
The exploration of chemical reactions preceding ignition is essential for the development of ideal hypergolic propellants. Unexpected reaction pathways of a hypergolic mixture composed of monomethylhydrazine and nitrogen dioxide are predicted through a cooperative combination of (i) spin-unrestricted ab initio molecular dynamics (AIMD) and (ii) wave packet dynamics of protons. Ensembles of AIMD trajectories reveal a sequence of reaction steps for proton transfer and rupture of the C-N bond. The details of proton transfer are explored by wave packet dynamics on the basis of ab initio potential energy surfaces from AIMD trajectories. The possibility of spontaneous ignition of this hypergolic mixture at room temperature is predicted as a quantized feature of proton-transfer dynamics.
探索点火前的化学反应对于开发理想的自燃推进剂至关重要。通过（i）自旋非限制从头算分子动力学（AIMD）和（ii）质子波包动力学的协同结合，预测了由一甲基肼和二氧化氮组成的自燃混合物的意外反应途径。AIMD轨迹集合揭示了质子转移和C-N键断裂的一系列反应步骤。基于AIMD轨迹的从头算势能面，通过波包动力学探索质子转移的细节。预测了这种自燃混合物在室温下自燃的可能性，这是质子转移动力学的一种量子化特征。
