Original Paper

Journal of Molecular Modeling

, Volume 18, Issue 7, pp 3363-3378

Molecular simulations of adsorption of RDX and TATP on IRMOF-1(Be)

  • Andrea Michalkova ScottAffiliated withU.S. Army Engineer Research and Development Center (ERDC)Interdisciplinary Nanotoxicity Center, Department of Chemistry, Jackson State University Email author 
  • , Tetyana PetrovaAffiliated withInterdisciplinary Nanotoxicity Center, Department of Chemistry, Jackson State University
  • , Khorgolkhuu OdbadrakhAffiliated withMaterials Science and Technology Division, Oak Ridge National Laboratory (ORNL)
  • , Donald M. NicholsonAffiliated withCenter for Nanophase Materials Sciences, and Computer Sciences and Mathematics Division, Oak Ridge National Laboratory
  • , Miguel Fuentes-CabreraAffiliated withCenter for Nanophase Materials Sciences, and Computer Sciences and Mathematics Division, Oak Ridge National Laboratory
  • , James P. LewisAffiliated withDepartment of Physics and Astronomy, West Virginia University
  • , Frances C. HillAffiliated withU.S. Army Engineer Research and Development Center (ERDC)
  • , Jerzy LeszczynskiAffiliated withInterdisciplinary Nanotoxicity Center, Department of Chemistry, Jackson State University

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Abstract

The influence of different sorption sites of isoreticular metal-organic frameworks (IRMOFs) on interactions with explosive molecules is investigated. Different connector effects are taken into account by choosing IRMOF-1(Be) (IRMOF-1 with Zn replaced by Be), and two high explosive molecules: 1,3,5-trinitro-s-triazine (RDX) and triacetone triperoxide (TATP). The key interaction features (structural, electronic and energetic) of selected contaminants were analyzed by means of density functional calculations. The interaction of RDX and TATP with different IRMOF-1(Be) fragments is studied. The results show that physisorption is favored and occurs due to hydrogen bonding, which involves the C-H groups of both molecules and the carbonyl oxygen atoms of IRMOF-1(Be). Additional stabilization of RDX and TATP arises from weak electrostatic interactions. Interaction with IRMOF-1(Be) fragments leads to polarization of the target molecules. Of the molecular configurations we have studied, the Be-O-C cluster connected with six benzene linkers (1,4-benzenedicarboxylate, BDC), possesses the highest binding energy for the studied explosives (-16.4 kcal mol-1 for RDX and -12.9 kcal mol-1 for TATP). The main difference was discovered to be in the preferable adsorption site for adsorbates (RDX above the small and TATP placed above the big cage). Based on these results, IRMOF-1 can be suggested as an effective material for storage and also for separation of similar explosives. Hydration destabilizes most of the studied adsorption systems by 1-3 kcal mol-1 but it leads to the same trend in the binding strength as found for the non-hydrated complexes.

http://static-content.springer.com/image/art%3A10.1007%2Fs00894-011-1338-3/MediaObjects/894_2011_1338_Figa_HTML.gif
Figure

RDX adsorbed on IRMOF-1(Be) (B97-D/6-31G(d))

Keywords

Adsorption B97-D IRMOF-1 RDX TATP