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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Accurate Prediction of Bond Dissociation Energies and Barrier Heights for High-Energy Caged Nitro and Nitroamino Compounds Using a Coupled Cluster Theory
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Accurate Prediction of Bond Dissociation Energies and Barrier Heights for High-Energy Caged Nitro and Nitroamino Compounds Using a Coupled Cluster Theory

机译：使用耦合簇理论，精确地预测高能笼和硝基氨基化合物的高能量笼和硝基氨基化合物的屏障高度

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摘要

Highly accurate theoretical values of bond energies and activation barriers of primary decomposition reactions are crucial for reliable predictions of thermal decomposition and detonation-related phenomena of energetic materials (EM). However, due to the prohibitive computational cost, high-level ab initio calculations had been impractical for a large number of important EMs, including, e.g., hexanitrohexaazaisowurtzitane (CL-20). In the present work, we obtained accurate bond dissociation energies and the activation barriers for primary decomposition reactions for a series of novel promising caged polynitroamino and polynitro EMs, viz., CL-20, TEX, octanitrocubane (ONC), and hexanitro derivatives of adamantane, using the recently proposed domain-localized pair natural orbitals (DLPNO) modifications of coupled cluster techniques. DLPNO-CCSD(T) allows for routine quadruple-zeta basis set quality coupled cluster calculations for the species comprised of similar to 30 non-H atoms. The benchmarks on a number of simpler congeners of CL-20 and ONC revealed that the DLPNO approach does not deteriorate the quality of the quadruple-zeta coupled cluster procedure. With the aid of this technique, the full set of gas-phase primary decomposition reactions for all 9 conformers of CL-20 was considered. For all species studied, C-NO2 or N-NO2 radical decomposition channels dominate over molecular counterparts. The best theoretical results reported in the literature so far, viz., density functional theory energies of nitro group radical elimination in CL-20 and ONC, underestimate the value by similar to 10 kcal mol(-1). We also present reliable and accurate gas-phase formation enthalpies for CL-20, ONC, and related species. In a more general sense, these results offer a new level of predictive computational kinetics for polynitro-caged energetic materials.
机译：键能和初级分解反应的活化能垒的高度准确的理论值是用于热分解和高能材料（EM）的爆轰有关的现象的可靠的预测是至关重要的。但是，由于过高的计算成本，高级别从头计算已经为大量的重要EMS，包括，例如，六硝基六氮杂异伍兹烷（CL-20）是不现实的。在目前的工作中，我们获得准确键离解能和用于初级分解反应的活化能垒为有前途的笼polynitroamino和多硝基EMS，即，CL-20，TEX，八硝基立方烷（ONC），和金刚烷的hexanitro衍生物一系列新的使用最近提出域本地化对天然轨道（DLPNO）的耦合群集技术的修改。 DLPNO-CCSD（T）允许常规四倍ζ电基组质量耦合簇计算对于由相似的30个非氢原子的物质。就一些CL-20和ONC的简单同源的基准显示，DLPNO方法不会降低四倍ζ电耦合簇过程的质量。利用这种技术，全套为CL-20的所有构象异构体9气相初级分解反应的助剂被认为。对于所研究的所有物种，C-NO2或N-NO2基团分解通道支配分子对应。最好理论结果在文献中报道，到目前为止，即，在CL-20和ONC硝基自由基消除密度泛函理论能量，通过类似于10千卡摩尔（-1）低估值。我们还存在可靠和准确的气相生成焓为CL-20，ONC，以及相关的物种。在更普遍的意义上说，这些结果提供多硝基笼饲养含能材料的预测计算动力学的一个新的水平。

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