A B3LYP and MP2(full) theoretical investigation into explosive sensitivity upon the formation of the molecule-cation interaction between the nitro group of RNOub>2 ub> (R = -CHub>3 ub>, -NHub>2 ub>, -OCHub>3 ub>) and Naup>+ u
- 作者：Cong-hua Hou
- 关键词：Explosive sensitivity ; Molecule&ndash ; cation interaction ; Trigger bond dissociation energy ; MP2(full)
- 刊名：Computational and Theoretical Chemistry
- 出版年：2012
- 期刊代码：pc22_2210271X
- 类别：ch
- 出版时间：1 July, 2012
- 卷：991
- 期：Complete
- 页码：107-115
- 文件大小：917 K
摘要
The changes of the bond dissociation energy of the trigger bond (C-NOub>2 ub>, N-NOub>2 ub> or O-NOub>2 ub>) and nitro group charge upon the formation of the molecule-cation interaction between the nitro group of RNOub>2 ub> (R = -CHub>3 ub>, -NHub>2 ub>, -OCHub>3 ub>) and cation (Naup>+ up>, Mgup>2+ up>, Alup>3+ up>) have been systematically investigated using the B3LYP and MP2(full) methods with the 6-311++Gup>** up>, 6-311++G(2d,p) and aug-cc-pVTZ basis sets. The trigger bond dissociation energy is the order of NM鈰疦aup>+ up> < NM鈰疢gup>2+ up> < NM鈰疉lup>3+ up>, NA鈰疦aup>+ up> < NA鈰疢gup>2+ up> < NA鈰疉lup>3+ up> and MN鈰疦aup>+ up> < MN鈰疢gup>2+ up>, respectively. The strength of the trigger bond is enhanced and the explosive sensitivity is reduced upon the formation of molecule-cation interaction. The increment of the trigger bond dissociation energy (螖BDE) in comparison with the monomer correlates well with the molecule-cation interaction energy Eub>int. ub>, electron density 蟻ub>BCP(O6鈰痗ation) ub>, delocalization energy and mulliken charge of the nitro group. The linear relationship between the mulliken charge of the nitro group in complex and the O6鈰痗ation distance or is also found. The analyzes of AIM, NBO and electron density shifts show that the electron density shifts toward the trigger bond upon the formation of the molecule-cation interaction. Thus, the trigger bond is strengthened and the sensitivity is reduced.