Christopher Imogen L, Michalchuk Adam A L, Pulham Colin R, Morrison Carole A
EaStCHEM School of Chemistry, University of Edinburgh, Edinburgh, United Kingdom.
Federal Institute for Materials Research and Testing (BAM), Berlin, Germany.
Front Chem. 2021 Jul 20;9:726357. doi: 10.3389/fchem.2021.726357. eCollection 2021.
The reliable determination of gas-phase and solid-state heats of formation are important considerations in energetic materials research. Herein, the ability of PM7 to calculate the gas-phase heats of formation for CNHO-only and inorganic compounds has been critically evaluated, and for the former, comparisons drawn with isodesmic equations and atom equivalence methods. Routes to obtain solid-state heats of formation for a range of single-component molecular solids, salts, and co-crystals were also evaluated. Finally, local vibrational mode analysis has been used to calculate bond length/force constant curves for seven different chemical bonds occurring in CHNO-containing molecules, which allow for rapid identification of the weakest bond, opening up great potential to rationalise decomposition pathways. Both metrics are important tools in rationalising the design of new energetic materials through computational screening processes.
可靠地测定气相和固态生成热是含能材料研究中的重要考量因素。在此，对PM7计算仅含CNHO的化合物和无机化合物的气相生成热的能力进行了严格评估，对于前者，与等键反应式和原子等效方法进行了比较。还评估了获得一系列单组分分子固体、盐和共晶体固态生成热的途径。最后，利用局部振动模式分析计算了含CHNO分子中出现的七种不同化学键的键长/力常数曲线，这有助于快速识别最弱键，为合理化分解途径开辟了巨大潜力。这两个指标都是通过计算筛选过程合理化新型含能材料设计的重要工具。
