硝基炸药分子间与分子内耦合作用机制及其声子谱学特征

Explosive energetic materials are key important to civil engineering, mining and railway construction, land security and national defense, and astronautic devices driving. Understanding the energy storage-release dynamics is very critical not only to knowledge creation but also to new energetic materials synthesis and design. We aim to extending our recent hydrogen bond relaxation theory, spectrometrics techniques, and associated progress on water and solutions to energetic materials study, with new perspectives. With the aid of quantum computation, Lagrangian mechanics, and phonon spectrometrics, we will prove the following proposals: 1) the functionality of the nonbonding electrons is critical; 2) the asymmetrical, short-range, and strongly correlated X:H-Y(X, Y = C,N,O) hydrogen bond like dictates the performance of the bonding network; 3) energy storage in the covalent bond deformed by X::Y super-hydrogen-bond compression; and 4) energy release by covalent bond relaxation and dissociation through X::Y destruction. We hope the practice inspires new ways of thinking and approach as well as interest and intelligence to explore the functionality of the energetic materials, providing foundations and analytical techniques for energetic materials development.

炸药是航空航天与国防安全等领域的关键材料,而透彻理解和精密诊断其微观储能机制是提高其性能的关键。本项目旨在拓展我们的键弛豫理论和计量谱学技术(Chem Rev 2015, 115: 6746-810; USA 2017 patent No. 9,625,397B2)探讨硝基炸药的分子间与分子内关联作用并证明我们提出的：1)以非键孤对电子“:”为主导的超常规配位键的弛豫控制炸药的储能和燃爆过程；2）X:H-Y类氢键的张弛拉伸与X::Y超氢键的排斥挤压相耦合不仅平衡分子间的相互作用(X,Y = C,N,O)而且压缩分子内共价键而储能；3)一旦处于拉伸状态的X:H非键受激破损，分子内受压共价键因逆向反弹弛豫而雪崩裂解释放能量。项目实施不仅完善现有价键理论以对炸药的认知与合成提供指导和诊断技术而且证明我们的超常配位键理论体系的完备和普适性。

此项目拓展我们的键弛豫理论和计量谱学技术探讨硝基炸药的分子间与分子内关联作用,并证明了我们提出的:1)以非键孤对电子“:”为主导的超常规配位键的弛豫控制炸药的储能和燃爆过程；2)X:H-Y类氢键的张弛拉伸与X::Y超氢键的排斥挤压相耦合不仅平衡分子间的相互作用(X,Y = C,N,O)而且压缩分子内共价键而储能；3)一旦处于拉伸状态的X:H非键受激破损,分子内受压共价键因逆向反弹弛豫而雪崩裂解释放能量.水的H-O键和TATB的H-N将显示负热胀系数和负压缩系数,而硝基甲烷的H-C键因O—C的排斥作用显示负热胀系数和正压缩系数.引入变温和变压微扰显著提升声子谱学技术的功能.研究结果证明了X:H-Y耦合氢键的受激极化和协同弛豫在水与氮基炸药具有普适性,并预期可拓展到食品、药物、以及生命健康的分子科学以及低维高温超导和超低配位催化反应过程[80, 81].在此项基金支持下培养2名硕士和1名博士,已发表SCI论文10余篇,专利两项,参加多次国内国际学术会议并做邀请报告.