ORIGINAL PAPER Molecular design and screening of energetic nitramine derivatives Alka Devi 1 & Sonal Deswal 1 & Srinivas Dharavath 2 & Vikas D. Ghule 1 Received: 4 September 2015 /Accepted: 19 October 2015 /Published online: 30 October 2015 # Springer-Verlag Berlin Heidelberg 2015 Abstract Six nitramines (N1–6) were designed with all pos- sible arrangements of N–NO 2 groups on a cyclic skeleton and structural optimization was performed using the density func- tional theory (DFT). We observed that all nitramines have high positive heats of formation proportionate to the number of N-NO 2 groups in their molecular structure. Among the designed nitramines, N5 and N6 have crystal densities of 1.77 and 1.81 g cm -3 , respectively, which lead to reasonable respective detonation velocities (D =8.70 and 9.07 km s -1 ) and detonation pressures (P =33.23 and 36.57 GPa) compara- ble to those of RDX. To understand the relationship between sensitivity and molecular structure, bond dissociation ener- gies, impact sensitivities (h 50 ), free space in crystal lattice, imbalance between the positive and negative surface poten- tials and heats of detonation (Q) were investigated. The com- parable performance of N5 and N6 with RDX highlights the potential application of these nitramine derivatives as high energy materials and also supports the advantage of N–N bonds in the backbone and substitution of N–NO 2 groups. Keywords Nitramine . Heat of formation . Detonation . Impact sensitivity . Bond dissociation energy Introduction The high stored energy and potential of energetic materials makes them well suited to propellant and explosive applica- tions [1–3]. The search for high performance energetic mate- rials with better stability and lower sensitivity is the main objective of energetic materials research and is a never- ending process [4–7]. Nitramine (N–NO 2 ) compounds are an important class of organic explosive, and are known to combine oxygen balance, density, performance and stability. In addition, previous reports have shown that introduction of a nitramine group into a molecule can increase its density and, thus, detonation performance [8–10]. 1,3,5-Trinitro-1,3,5- triazacyclohexane (RDX), 1,3,5,7-tetranitro-1,3,5,7- tetraazacyclooctane (HMX), and 2,4,6,8,10,12-hexanitro-2,4, 6,8,10,12-hexaazaisowurtzitane (CL-20) are the most signifi- cant members of this class of compounds. Most nitramines have higher shattering capability and chemical resistance compared to their nitrate ester analogs [11]. RDX and HMX are the most extensively used military explosives; however, they have the risk of quick detonation and catastrophic explo- sion if used in high caliber guns and in the magazines of ships [11]. Similarly, CL-20 is superior in detonation performance but has limited explosive application due to its high sensitiv- ity. In this article, we present six new nitramine molecules containing an octahydro[1, 2, 4, 5]tetrazino[1,2-a][1,2,4, 5]tetrazine (OHTT) backbone, which were designed to achieve the high performance characteristics derived from cy- clic structure and nitramine groups. The designed molecular structures are shown in Fig. 1. The OHTT ring has been re- ported in the literature (see Fig. S1 in Supporting Information) [12]; however, its nitramine derivatives have not been cited in experimental or theoretical studies. Owing to the difficulties in synthesis of the hypothetical molecules, a known strategy for the preparation of OHTT ring with four N–H sites also Electronic supplementary material The online version of this article (doi:10.1007/s00894-015-2846-3) contains supplementary material, which is available to authorized users. * Vikas D. Ghule gvd@nitkkr.ac.in 1 Department of Chemistry, National Institute of Technology, Kurukshetra 136119, Haryana, India 2 Advanced Centre of Research in High Energy Materials (ACRHEM), University of Hyderabad, Hyderabad 500046, India J Mol Model (2015) 21: 298 DOI 10.1007/s00894-015-2846-3