Are HOMO-LUMO gaps reliable indicators of explosive impact sensitivity?

Autor: Politzer P; Department of Chemistry, University of New Orleans, New Orleans, LA, 70148, USA. ppolitze@uno.edu., Murray JS; Department of Chemistry, University of New Orleans, New Orleans, LA, 70148, USA.
Jazyk: angličtina
Zdroj: Journal of molecular modeling [J Mol Model] 2021 Oct 23; Vol. 27 (11), pp. 327. Date of Electronic Publication: 2021 Oct 23.
DOI: 10.1007/s00894-021-04956-1
Abstrakt: A high priority in designing and evaluating proposed explosives is to minimize sensitivity, i.e., vulnerability to unintended detonation due to an accidental stimulus, such as impact. In order to establish a capability for predicting impact sensitivity, there have been numerous attempts to correlate it with some molecular or crystal property or properties. One common approach has been to relate impact sensitivity to the difference between the energies of the highest-occupied and lowest-unoccupied molecular orbitals of the explosive molecule, the "HOMO-LUMO gap." In the present study, we tested this approach for a series of twelve explosive nitroaromatics, using four different computational methods. We found that the HOMO-LUMO gap does not appear to be a reliable indicator of relative impact sensitivity. Since detonation initiation involves a series of steps, all of which influence sensitivity; it seems more realistic to try to identify fundamental factors and general trends related to sensitivity ‒ an approach that has already had some success ‒ rather than to seek correlations with one or two specific properties.
(© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)
Databáze: MEDLINE
Externí odkaz: