Ab initio calculation of ionization potential and electron affinity of six common explosive compounds
Jason K Cooper,1 Christian D Grant,2 Jin Z Zhang1
1Department of Chemistry and Biochemistry, University of California, Santa Cruz, CA, 2Physical and Life Sciences, Chemical Sciences Division, Lawrence Livermore National Laboratory, Livermore, CA, USA
Abstract: The vertical and adiabatic ionization potential (IPV and IPA) and vertical electron affinity (EAV) for six explosives, hexogen (RDX), octogen (HMX), triacetone triperoxide (TATP), hexamethylene triperoxide diamine (HMTD), 2,4,6-trinitrotoluene (TNT), and pentaerythritol tetranitrate (PETN), have been studied using ab initio computational methods. The IPV was calculated using MP2, CBS-QB3, and Koopmans’ theory, while the IPA was calculated with B3LYP, CAM-B3LYP, ψB97XD, B2PLYP, and MP2 using the ΔE method for the ground state B3LYP optimized geometries. IPAs of RDX and TNT were also calculated using CBS-QB3 with relaxed geometries of the ions. Of the methods tested, B3LYP and B2PLYPD provided superior and more consistent results for calculating the IP compared to CBS-QB3 level IPA calculations and experimental data (where available). CBS-QB3 was used as a benchmark for calculating the EAV as experimental data has not been reported. For calculations of the EAV, B3LYP performed the worst while MP2 and B2PLYPD predicted values closest to those made by CBS-QB3. Basis set effects were evaluated using 6-31+G(d,p), 6-311+G(d,p), and 6-311+G(3df,2p) for both IP and EA. 6-31+G(d,p) gave satisfactory results for calculating IP while 6-311+G(3df,2p) had improved results for calculating the EA. The four nitro-containing compounds have exothermic reduction potentials while the peroxides are endothermic. In addition, it was determined that RDX, HMX, TATP, and HMTD had unstable geometries in their reduced forms. The results should be useful in developing detection and screening methods including ionization methods for mass spectroscopy and fluorescence quenching methods of detection.
Keywords: ionization, affinity, explosive, TNT, ab initio, DFT
© 2012 The Author(s). This work is published and licensed by Dove Medical Press Limited. The full terms of this license are available at https://www.dovepress.com/terms.php and incorporate the Creative Commons Attribution - Non Commercial (unported, v3.0) License. By accessing the work you hereby accept the Terms. Non-commercial uses of the work are permitted without any further permission from Dove Medical Press Limited, provided the work is properly attributed. For permission for commercial use of this work, please see paragraphs 4.2 and 5 of our Terms.