Structure and redox properties of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) adsorbed on a silica surface. A DFT M05 computational study

Liudmyla K. Sviatenko, Leonid Gorb, Sergiy Okovytyy, Jerzy Leszczynski


Adsorption of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) on (001) surface of α-quartzwas studiedat the M05/tzvp level using cluster approximation. Hydrogen bonds between nitramines and silica surface were analyzed by atoms in molecules (AIM) method. Electron attachment causes significant change in geometry of adsorbed complexes. Redox properties of adsorbed RDX and HMX were compared with those of gas-phase and hydrated species by calculation of the ionization potential, electron affinity, oxidation and reduction Gibbs free energies, oxidation and reduction potentials. Calculations show that adsorbed RDX and HMX have lower ability to undergo redox transformations than hydrated ones.


silica, RDX, HMX, adsorption, reduction, oxidation

Full Text:



U.S. department of health and human services. Public Health Service Agency for Toxic Substances and Disease Registry (2012). Toxicological profile for RDX, Georgia, 174 p.

Felt, D., Johnson, J. L., Larson, S., Hubbard, B., Henry, K., Nestler, C., Ballard, J. H. (2013). Evaluation of Treatment Technologies for Wastewater from Insensitive Munitions Production. ERDC/EL TR-13-20 Environmental Laboratory, US Army Engineer Research and Development Center, Vicksburg, MS.

Lin, K. S., Dehvari, K., Hsien, M. J., Hsu, P. J., Kuo, H. (2013). Degradation of TNT, RDX, and HMX explosive waste-waters using zero-valent iron nanoparticles. Propellants Explos. Pyrotech., 38, 786–90. doi: 10.1002/prep.201200205 CrossRef

Jiao, W., Guo, L., Liu, Y. Z., Liu, W. L., Li, J., Xu, C.C. (2014). Degradation of HMX production wastewater by fenton oxidation. Chinese J. Energ. Mater., 22(1), 94–99. doi: 10.3969/j.issn.1006–9941.2014.01.020 CrossRef

Sharma, P., Mayes, M. A., Tang, G. (2013). Role of soil organic carbon and colloids in sorption and transport of TNT, RDX and HMX in training range soils. Chemosphere, 92(8), 993–1000. doi: 10.1016/j.chemosphere.2013.03.028 CrossRef

Hatzinger, P. B.; Fuller, M. E., Rungmakol, D., Schuster, R. L., Steffan, R. J. (2004). Enhancing the attenuation of explosives in surface soils at military facilities: sorption-desorption isotherms. Environ. Toxicol. Chem., 23, 306–312. doi: 10.1897/03-186 CrossRef

Ariyarathna, T., Vlahos, P., Tobias, C., Smith, R. (2016). Sorption kinetics of TNT and RDX in anaerobic freshwater and marine sediments: Batch studies. Environ. Toxicol. Chem., 35(1), 47–55. doi: 10.1002/etc.3149 CrossRef

Katseanes, C. K., Chappell M. A., Hopkins, B. G., Durham, B. D., Price, C. L., Porter, B. E., Miller, L. F. (2016). Multivariate functions for predicting the sorption of 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitro-1,3,5-tricyclohexane (RDX) among taxonomically distinct soils. J. Environ. Manag., 182, 101–110. doi: 10.1016/j.jenvman.2016.07.043 CrossRef

Sviatenko, L. K., Isayev, O., Gorb, L., Hill, F. C., Leszczynska, D., Leszczynski, J. (2015). Are the reduction and oxidation properties of nitrocompounds dissolved in water different from those produced when adsorbed on a silica surface? An DFT M05-2X computational study. J. Comput. Chem., 36(14), 1029–1035. doi: 10.1002/jcc.23878 CrossRef

Sviatenko, L. K., Gorb, L., Okovytyy, S. I. (2015). Structure and redox properties of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) adsorbed on a silica surface. M05 computational study. Bull. Dnipropetrovsk Univ. Ser. Chem., 23(2),1–9. doi: 10.15421/081511 CrossRef

Sviatenko, L. K., Gorb, L., Hill, F. C., Leszczynska, D., Leszczynski, J. (2015). ANTA structure and redox properties of 5-amino-3-nitro-1H-1,2,4-triazole (ANTA) adsorbed on a silica surface: A DFT M05 computational study. J. Phys. Chem. A., 119(29), 8139–8145. doi: 10.1021/acs.jpca.5b03393 CrossRef

Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G. A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H. P., Izmaylov, A. F., Bloino, J., Zheng, G., Sonnenberg, J. L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, Jr., J. A., Peralta, J. E., Ogliaro, F., Bearpark, M., Heyd, J. J., Brothers, E., Kudin, K. N., Staroverov, V. N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J. C., Iyengar, S. S., Tomasi, J., Cossi, M., Rega, N., Millam, J. M., Klene, M., Knox, J. E., Cross, J. B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R. E., Yazyev, O., Austin, A. J., Cammi, R., Pomelli, C., Ochterski, J. W., Martin, R. L., Morokuma, K., Zakrzewski, V. G., Voth, G. A., Salvador, P., Dannenberg, J. J., Dapprich, S., Daniels, A. D., Farkas, O., Foresman, J. B., Ortiz, J. V., Cioslowski, J., Fox, D. J. (2009). Gaussian 09 (Revision A.02) [Computer software]. Gaussian Inc., Wallingford CT.

Lu, T., Chen, F. (2012). Multiwfn: A multifunctional wavefunction analyzer. J. Comput. Chem., 33, 580–592. doi: 10.1002/jcc.22885 CrossRef

Truhlar, D., Cramer, C., Lewis, A., Bumpus, J. (2004). Molecular modeling of environmentally relevant processes: reduction potentials. J. Chem. Ed., 81, 596–604. doi: 10.1021/ed081p596 CrossRef

Molt, Jr. R. W., Watson, Jr. T., Bazante, A. P., Bartlett, R. J. (2013). The great diversity of HMX conformers: probing the potential energy surface using CCSD(T). J. Phys. Chem. A, 117, 3467−3474. doi: 10.1021/jp311073m CrossRef

Al-Saidi, W. A., Asher, S. A., Norman, P. (2012). Resonance Raman spectra of TNT and RDX using vibronic theory, excited-state gradient, and complex polarizability approximations. J. Phys. Chem. A, 116, 7862−7872. doi: 10.1021/jp303920c CrossRef



  • There are currently no refbacks.

Comments on this article

View all comments

Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 International License.

eISSN: 2313-4984 | pISSN: 2306-871X
The journal publishes research papers on terms: Creative Commons Attribution 4.0 International License
Founder: Oles Honchar Dnipropetrovsk National University