Aina, AA;
Misquitta, AJ;
Phipps, MJS;
Price, SL;
(2019)
Charge Distributions of Nitro Groups Within Organic Explosive Crystals: Effects on Sensitivity and Modeling.
ACS Omega
, 4
(5)
pp. 8614-8625.
10.1021/acsomega.9b00648.
Preview |
Text
Price_Charge Distributions of Nitro Groups Within Organic Explosive Crystals. Effects on Sensitivity and Modeling_VoR.pdf - Published Version Download (3MB) | Preview |
Abstract
The charge distribution of NO2 groups within the crystalline polymorphs of energetic materials strongly affects their explosive properties. We use the recently introduced basis-space iterated stockholder atom partitioning of high-quality charge distributions to examine the approximations that can be made in modeling polymorphs and their physical properties, using 1,3,5-trinitroperhydro-1,3,5-triazine, trinitrotoluene, 1-3-5-trinitrobenzene, and hexanitrobenzene as exemplars. The NO_{2} charge distribution is strongly affected by the neighboring atoms, the rest of the molecules, and also significantly by the NO2 torsion angle within the possible variations found in observed crystal structures. Thus, the proposed correlations between the molecular electrostatic properties, such as trigger-bond potential or maxima in the electrostatic potential, and impact sensitivity will be affected by the changes in conformation that occur on crystallization. We establish the relationship between the NO_{2} torsion angle and the likelihood of occurrence in observed crystal structures, the conformational energy, and the charge and dipole magnitude on each atom, and how this varies with the neighboring groups. We examine the effect of analytically rotating the atomic multipole moments to model changes in torsion angle and establish that this is a viable approach for crystal structures but is not accurate enough to model the relative lattice energies. This establishes the basis of transferability of the NO2 charge distribution for realistic nonempirical model intermolecular potentials for simulating energetic materials.
| Type: | Article |
|---|---|
| Title: | Charge Distributions of Nitro Groups Within Organic Explosive Crystals: Effects on Sensitivity and Modeling |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1021/acsomega.9b00648 |
| Publisher version: | https://doi.org/10.1021/acsomega.9b00648 |
| Language: | English |
| Additional information: | © 2019 American Chemical Society. This is an open access article published under a Creative Commons Attribution (CC-BY) License (https://creativecommons.org/licenses/by/4.0/). |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery.ucl.ac.uk/id/eprint/10075667 |
Archive Staff Only
 |
View Item |
