Prediction of the crystal packing of di‐tetrazine‐tetroxide (DTTO) energetic material. Issue 2 (18th March 2015)

• Record Type: Journal Article
• Authors: Mendoza‐Cortes, Jose L.; An, Qi; Goddard, William A.; Ye, Caichao; Zybin, Sergey
• Is Part Of: Journal of computational chemistry. Volume 37:Issue 2(2016)
• Page Start: 163
• Page End: 167
• Publication Date: 2015-03-18
• Subjects: crystal structure prediction -- density functional theory -- PBE‐ulg -- Monte Carlo sampling -- energetic materials; Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.23893
• Languages: English
• ISSNs: 0192-8651

Abstract

Abstract : Previous calculations suggested that di‐tetrazine‐tetroxide (DTTO), aka tetrazino‐tetrazine‐tetraoxide, might have a particularly large density (2.3 g/cm 3 ) and high energy release (8.8 kJ/kg), but it has not yet been synthesized successfully. We report here density functional theory (DFT) (M06, B3LYP, and PBE‐ulg) on 20 possible isomers of DTTO. For the two most stable isomers, c1 andc2 we predict the best packings (i.e., polymorphs) among the 10 most common space groups for organic molecular crystal using the Universal force field and Dreiding force field with Monte Carlo sampling. This was followed by DFT calculations at the PBE‐ulg level to optimize the crystal packing. We conclude that thec1 isomer has the P21 21 21 space group with a density of 1.96 g/cm 3, while thec2 isomer has the Pbca space group with a density of 1.98 g/cm 3 . These densities are among the highest of current energetic materials, RDX (1.81 g/cm 3 ) and CL20 (2.01 g/cm 3 ). We observe that the stability of the polymorphs increases with the density while the planarity decreases. © 2015 Wiley Periodicals, Inc. Abstract : The two most stable isomers of Di‐tetrazine‐tetroxide (DTTO), c1 andc2, were used to predict the most stable polymorphs of DTTO. For thec1 isomer, the most stable polymorph is the P21 21 21 space group with a density of 1.96 g/cm 3 . Conversely, for thec2 isomer, the most stable polymorph is the Pbca space group with a density of 1.98 g/cm 3 . These predicted densities are among the highest of current energetic materials.