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HMX/DMF溶剂化物结构和分子间相互作用的理论研究
引用本文:段晓惠,于海利,陈杰,李洪珍.HMX/DMF溶剂化物结构和分子间相互作用的理论研究[J].含能材料,2012,20(4):454-458.
作者姓名:段晓惠  于海利  陈杰  李洪珍
作者单位:西南科技大学,西南科技大学,西南科技大学,西南科技大学
基金项目:国家自然科学基金项目(面上项目,重点项目,重大项目); 四川省教育厅重点科研项目
摘    要:采用量子化学计算和分子动力学(MD)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β-HMX分子的MD模拟表明,HMX的分子构象已经从β转变为α相。在M P2/6-31G*水平上的理论计算也说明,在D M F溶剂中,α-HM X比β-HM X更稳定。这解释了在HM X/D M F溶剂化物的多晶型中,所有的HMX分子均呈α构象的原因。采用MP2/6-31G*方法,对α-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α-HMX/DMF的稳定化能非常接近α-HMX/α-HMX,并远远大于D M F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α-HM X在D M F中的过饱和溶液的M D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HM X的D M F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。

关 键 词:物理化学  HMX  构象  稳定化能  C—H…O氢键  共结晶
收稿时间:2011/10/25 0:00:00
修稿时间:5/17/2012 3:22:14 PM

Theoretical investigation on structure and intermolecular interaction for HMX/DMF solvate
Duan Xiao-hui,Yu Hai-li,Chen Jie and Li Hong-zhen.Theoretical investigation on structure and intermolecular interaction for HMX/DMF solvate[J].Chinese Journal of Energetic Materials,2012,20(4):454-458.
Authors:Duan Xiao-hui  Yu Hai-li  Chen Jie and Li Hong-zhen
Affiliation:College of materials science and Engineering, Southwest University of Science and Technology,College of materials science and Engineering, Southwest University of Science and Technology,College of materials science and Engineering, Southwest University of Science and Technology,Institute of Chemical Materials, Chinese Academy of Engineering Physics
Abstract:The structures and intermolecular interactions for octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX)/N,N-dimethylformamide(DMF) solvate have been investigated through quantum chemistry calculations and molecular dynamics(MD) simulations.MD simulation for a β-HMX molecule immersed in DMF solvent shows that β conformation has been transformed into α form.Theoretical calculations at the MP2/6-31G* level also indicate that the α-HMX is more stable than β-HMX in DMF solution.This explains why all HMX molecules present α-form in the polymorphic forms of HMX/DMF solvate.Geometrical optimizations at the level of MP2/6-31G* are performed for all the possible homodimers and heterodimers between α-HMX and DMF.Results reveal that C—H…O hydrogen bond interactions exist between components.Moreover,the stabilization energy of α-HMX/DMF is very close to that of α-HMX/α-HMX and much larger than that of DMF dimer.This means that the heteromeric intermolecular forces can compete with the homomeric intermolecular forces,and co-crystallization is possible to occur from the thermodynamics viewpoint.MD simulation for the supersaturation solution of α-HMX in DMF presents the intermolecular interactions is in favor of co-crystallization.These theoretical investigations provide valuable information for understanding why there occurs co-crystallization other than re-crystallization in DMF solution of HMX.
Keywords:physical chemistry  conformation  stabilization energy  C—H…O hydrogen bond  co-crystallization
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