Understanding the solubility of triamino-trinitrobenzene in hydrous tetramethylammonium fluoride: A first principles molecular dynamics simulation study

Bhabani S. Mallik, I. F William Kuo, Laurence E. Fried, J. Ilja Siepmann

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13 Scopus citations

Abstract

With the aim to understand the relatively high solubility of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), an important energetic material with a high degree of inter- and intra-molecular hydrogen bonding, in fluoride anion containing ionic liquids (ILs), first principles molecular dynamics simulations in the isobaric-isothermal ensemble were carried out for a system using hydrous tetramethylammonium fluoride as the prototypical solvent. Simulations initiated from both molecular TATB and its Meisenheimer complex (i.e., a σ-complex of the fluoride and the electrophilic ring of TATB) yield a Zundel-type complex where a proton is shared between an amino group and an F - ion, whereas the Meisenheimer complex is found to be only transiently stable. An analysis of the electronic structure probing the Wannier function centers supports the finding of a proton-sharing complex with a three-center four-electron like bond. The Zundel-type complex also yields an electronic absorption spectrum consistent with the experimentally observed color change. This study provides evidence that the remarkable solubility of otherwise hard-to-dissolve molecular crystals in ILs can be aided by chemical modification of the solute.

Original languageEnglish (US)
Pages (from-to)4884-4890
Number of pages7
JournalPhysical Chemistry Chemical Physics
Volume14
Issue number14
DOIs
StatePublished - Apr 14 2012

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