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含能材料  2012 

HMX/DMF溶剂化物结构和分子间相互作用的理论研究(英文)

DOI: 10.3969/j.issn.1006-9941.2012.04.016

Keywords: :物理化学,HMX,构象,稳定化能,C–H…O氢键,共结晶.

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Abstract:

采用量子化学计算和分子动力学模拟,研究了溶剂化物环四亚甲基四硝胺(HMX)/N,N–二甲基甲酰胺(DMF)的结构和分子间相互作用。对浸渍在DMF溶剂中的?–HMX分子的MD模拟表明,HMX的分子构象已经从?相变为?相。在MP2/6–31G*水平上的理论计算也说明,在DMF溶剂中,?–HMX比?–HMX更稳定。这解释了在HMX/DMF溶剂化物的多晶型中,为什么所有的HMX分子均呈?构象。采用MP2/6–31G*方法,对?–HMX和DMF分子间可能的同型和异型二聚体进行结构优化。结果表明,组分间存在C–H…O氢键相互作用。并且?–HMX/DMF的稳定化能非常接近?–HMX/?–HMX,并远远大于DMF二聚体的。这意味着异型分子间力可和同型分子间力竞争。从热力学的观点来看,共结晶过程可能发生。对?–HMX在DMF中的过饱和溶液的MD模拟表明,分子间相互作用对共结晶有利。这些理论研究对理解在HMX的DMF溶液中为什么发生的是共结晶而不是重结晶提供了有价值的信息。

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