论文标题
铝二异丙基甲基膦酸酯（DIMP）在氧化铝上的高温分解：从头开始分子动力学的机械预测
High-Temperature Decomposition of Diisopropyl Methylphosphonate (DIMP) on Alumina: Mechanistic Predictions from Ab Initio Molecular Dynamics
论文作者
论文摘要
金属氧化物表面上基于有机磷的化学战剂（CWAS）的降解增强，对中和努力持巨大希望。但是，此过程中的基本机制仍然很少理解。我们首次利用大规模量子计算来探测二异丙基甲基膦酸酯（DIMP）的高温降解，一种神经剂模拟剂。我们出生的烟囱分子动力学（BOMD）计算表明，$γ$ -AL $ _2 $ o $ _3 $表面表现出巨大的希望，可以快速吸引和破坏CWAS。我们发现，氧化铝表面在所有温度下迅速吸附DIMP，随后DIMP的分解通过丙烯消除进行。我们的BOMD计算与元动力学模拟相辅相成，以产生自由能路径，这表明激活屏障随温度而降低，并且DIMP很容易分解为$γ$ -AL $ _2 $ o $ $ _3 $。我们的第一原则BOMD和元动力学模拟为SARIN分解模型和机械信息提供了至关重要的诊断，以检查其他候选金属氧化物表面上的CWA分解反应。
The enhanced degradation of organophosphorous-based chemical warfare agents (CWAs) on metal-oxide surfaces holds immense promise for neutralization efforts; however, the underlying mechanisms in this process remain poorly understood. We utilize large-scale quantum calculations for the first time to probe the high-temperature degradation of diisopropyl methylphosphonate (DIMP), a nerve agent simulant. Our Born-Oppenheimer molecular dynamics (BOMD) calculations show that the $γ$-Al$_2$O$_3$ surface shows immense promise for quickly adsorbing and destroying CWAs. We find that the alumina surface quickly adsorbs DIMP at all temperatures, and subsequent decomposition of DIMP proceeds via a propene elimination. Our BOMD calculations are complemented with metadynamics simulations to produce free energy paths, which show that the activation barrier decreases with temperature and DIMP readily decomposes on $γ$-Al$_2$O$_3$. Our first-principle BOMD and metadynamics simulations provide crucial diagnostics for sarin decomposition models and mechanistic information for examining CWA decomposition reactions on other candidate metal oxide surfaces.
