Theoretical prediction on heats of formation for polyisocyanocubanes |
| |
Authors: | Xiao Heming and Zhang Ji |
| |
Institution: | (1) Department of Chemistry, Nanjing University of Science and Technology, 210094 Nanjing, China |
| |
Abstract: | The heats of formation (HOF) for all the 21 polyisocyanocubanes are calculated systematically with density functional theory
(DFT) B3LYP and semiempirical MO(MINDO/3, MNDO, AM1 and PM3) methods. First, the accurate HOFs for the 8 title compounds are
obtained by means of designed isodesmic reactions at DFT-B3LYP/6-31G* level, and the cubane cage skeleton has not been broken
(i.e. choosing cubane as a reference compound) to produce more accurate and reliable results. It is found that there are good
linear relationships between the HOFs calculated using the B3LYP/6-31G* and four semiempirical MO methods, respectively, and
all of the linear correlation coefficients are more than 0.9971. The HOFs obtained from PM3 calculation are the best among
the four semiempirical MO methods. Then, the accurate HOFs at B3LYP/6-31G* level of other 13 polyisocyanocubanes are obtained
by systematically correcting their PM3-calculated HOFs. Polyisocyanocubanes have very high HOFs, and the HOFs increase linearly
with the increasing of the number of isocyano groups in a molecule. The results show that polyisocyanocubanes are the new
generation explosives with highly potential and exploitable value. |
| |
Keywords: | polyisocyanocubane heat of formation density functional theory(DFT) isodesmic reaction |
本文献已被 SpringerLink 等数据库收录! |
|