Assessment of various DFT, DFT-D, and MP2 methods
for studying FOX-7 detonation properties
Received: 30 May 2017 /Accepted: 19 July 2017 /Published online: 2 August 2017
Springer-Verlag GmbH Germany 2017
Abstract B3LYP, PBE, M06-2X, B2PLYP, BN2PLYP-D,
ωB97X-D, and MP2 levels of theory, in combination with
the 6–311++G(d,p) and cc-pVTZ basis sets were comprehen-
sively assessed for their ability to reproduce experimental
FOX-7 structural and detonation data. ωB97X-D/cc-pVTZ,
B3LYP/cc-pVTZ, and M06-2X/cc-pVTZ provided highly ac-
curate optimized structure predictions. M06-2X/cc-pVTZ and
ωB97X-D/cc-pVTZ reproduced experimentally determined
detonation properties (detonation velocity and detonation pres-
sure) with high accuracy. The results of this study demonstrate
that more accurate structure calculation levels provide more
reliable detonation property predictions. Moreover, the results
show that detonation property prediction is largely dependent
on the calculation level. This investigation demonstrates that
using a wide range of calculation levels enables the reliable
prediction and modeling of novel types of HEDMs.
Keywords Quantum calculation
High energy and density
With the development of wave function theories, such as HF
and MP2 methods, and various density functional theories
(DFTs), quantum calculations have been widely used to model
detonation properties and to design novel high energy and
density materials (HEDMs). These theoretical models enable
topological analysis and reduce the need to synthesize hazard-
ous materials [1, 2].
Recently, a number of groups have used theoretical methods
to design novel HEDMs based on several well-known explo-
sives (Fig. 1). Many reports have focused on the prediction of
the detonation properties of modified explosives. Moreover,
some of these studies have incorporated the effects of the ex-
ternal environment on explosives, which has been made pos-
sible by quantum calculations and simulations [3–7].
Most previous studies have been based on DFT methods
(typically B3LYP) with various basis sets [2–14]. Those stud-
ies are based on normal organic material calculation levels.
Therefore, for explosives that can form hydrogen bonds, it is
necessary to conduct calculations based on many different
DFT calculation levels, because of the high proportion of ni-
trogen and oxygen atoms in their chemical structures.
Diamino-2,2-dinitroethene (FOX-7) exhibits high explo-
sive performance and low sensitivity. The beneficial proper-
ties of FOX-7 result from the formation of strong inter- and
intramolecular hydrogen bonds, which stabilize FOX-7 mol-
ecules and reduce its sensitivity. The properties of FOX-7
have been experimentally investigated since 1998 .
However, it has only been studied theoretically using a small
range of methods [3, 10, 15–17]. Because MP2 typically re-
quires a much higher computational effort, DFT methods are
attractive alternatives. Recently, several DFT methods have
been proposed to correct long-range and dispersion interac-
tions . However, to compare the accuracies of theoretical
models, considerable quantum mechanical calculation studies
need to be carried out.
In the present study, HF and various popular DFT, DFT-D,
and MP2 methods with reliable basis sets were used to explore
Electronic supplementary material The online version of this article
(doi:10.1007/s00894-017-3427-4) contains supplementary material,
which is available to authorized users.
* Keunhong Jeong
Department of Chemistry and WMD & Energy Research Laboratory,
Korea Military Academy, Seoul 01805, Republic of Korea
J Mol Model (2017) 23: 250