中国物理B ›› 2014, Vol. 23 ›› Issue (6): 63103-063103.doi: 10.1088/1674-1056/23/6/063103

• ATOMIC AND MOLECULAR PHYSICS • 上一篇    下一篇

Theoretical studies on a series of nitroaliphatic energetic compounds

曾晖, 赵俊   

  1. School of Physical Science and Technology, Yangtze University, Jingzhou 434023, China
  • 收稿日期:2013-09-11 修回日期:2013-12-03 出版日期:2014-06-15 发布日期:2014-06-15
  • 基金资助:
    Project supported by the National Natural Science Foundation of China (Grant Nos. 11304022 and11347010), the Research Foundation of Education Bureau of Hubei Province, China (Grant Nos. Q20131208, T201204, and XD2014069), the Foundation of Yangtze University for Outstanding Young Teachers, China (Grant Nos. cyq201321 and cyq201322), and the Project for Basic Subjects (Grant No. 2013cjp10).

Theoretical studies on a series of nitroaliphatic energetic compounds

Zeng Hui (曾晖), Zhao Jun (赵俊)   

  1. School of Physical Science and Technology, Yangtze University, Jingzhou 434023, China
  • Received:2013-09-11 Revised:2013-12-03 Online:2014-06-15 Published:2014-06-15
  • Contact: Zhao Jun E-mail:zhaojun@yangtzeu.edu.cn
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Grant Nos. 11304022 and11347010), the Research Foundation of Education Bureau of Hubei Province, China (Grant Nos. Q20131208, T201204, and XD2014069), the Foundation of Yangtze University for Outstanding Young Teachers, China (Grant Nos. cyq201321 and cyq201322), and the Project for Basic Subjects (Grant No. 2013cjp10).

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摘要： Density functional theory calculations at the B3LYP/6-311G** level are performed to study the geometric and electronic structures of a series of nitroaliphatic compounds. The heats of formation (HOF) are predicted through the designed isodesmic reactions. Thermal stabilities are evaluated via the homolytic bond dissociation energies (BDEs). Further, the correlation is developed between impact sensitivity h50% and the ratio (BDE/E) of the weakest BDE to the total energy E containing zero point energy correction. In addition, the relative stability of the title compounds is evaluated based on the analysis of calculated Mulliken population and the energy gaps between the frontier orbitals. The calculated BDEs, HOFs, and energy gaps consistently indicate that compound 1,1,1,6,6,6-hexanitro-3-hexyne is the most unstable and the compound 3,3,4,4,-tetranitro-hexane is the most stable. These results provide basic information for the molecular design of novel high energetic density materials.

关键词: density functional theory, heats of formation, bond dissociation energy, isodesmic reaction

Abstract: Density functional theory calculations at the B3LYP/6-311G** level are performed to study the geometric and electronic structures of a series of nitroaliphatic compounds. The heats of formation (HOF) are predicted through the designed isodesmic reactions. Thermal stabilities are evaluated via the homolytic bond dissociation energies (BDEs). Further, the correlation is developed between impact sensitivity h50% and the ratio (BDE/E) of the weakest BDE to the total energy E containing zero point energy correction. In addition, the relative stability of the title compounds is evaluated based on the analysis of calculated Mulliken population and the energy gaps between the frontier orbitals. The calculated BDEs, HOFs, and energy gaps consistently indicate that compound 1,1,1,6,6,6-hexanitro-3-hexyne is the most unstable and the compound 3,3,4,4,-tetranitro-hexane is the most stable. These results provide basic information for the molecular design of novel high energetic density materials.

Key words: density functional theory, heats of formation, bond dissociation energy, isodesmic reaction

中图分类号: 

  • 31.15.E-
82.60.Cx (Enthalpies of combustion, reaction, and formation) 33.15.Fm (Bond strengths, dissociation energies) 82.20.-w (Chemical kinetics and dynamics)