Adsorption of dimethyl methylphosphonate and trimethyl phosphate on calcium oxide: An ab initio study

Y. Paukku, A. Michalkova, J. Leszczynski

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Ab initio study of the adsorption of dimethyl methylphosphonate (DMMP) and trimethyl phosphate (TMP) on three types of models simulating the calcium oxide surface (non-hydroxylated Ca4O4, completely hydroxylated Ca4O4(OH)2H2, and partially hydroxylated Ca4O4(OH)H) was performed. The target molecule and the surface hydroxyl groups were optimized while the CaO fragment was kept frozen. The intermolecular interactions were investigated applying Bader's Atoms in Molecules theory. The maps of electrostatic potential of the studied adsorption systems were also produced. The interaction energies of studied adsorption systems corrected by the basis set superposition error were obtained. The most energetically favorable adsorption of DMMP and TMP was found at the configuration where the oxygen atoms of the P=O and methoxy groups point toward the Ca cation of the surface. The P atom points toward the O atom of the surface and forms a P-O chemical bond. This configuration was revealed for the non-hydroxylated and partially hydroxylated CaO-DMMP and CaO-TMP systems. The presence and number of surface hydroxyl groups on the CaO models play a key role in the adsorption of the studied compounds. DMMP and TMP were found to be much less stable on the completely hydroxylated CaO surface where they are adsorbed only via weak electrostatic interactions and H-bonding to the surface oxygen atoms and hydroxyl groups. TMP was found to be slightly more stable on this type of surface than DMMP. The difference in stability is even larger if one compares this TMP system with the complex of tabun adsorbed on completely hydroxylated CaO surface model (Michalkova et al. Chem Phys Lett 438:72, 2007).

Original languageEnglish (US)
Pages (from-to)307-320
Number of pages14
JournalStructural Chemistry
Issue number2
StatePublished - Apr 2008

Bibliographical note

Funding Information:
Acknowledgments This work was facilitated by the support of the Chemical Materials Computational Modeling (CMCM) funded by the Department of Defense through the U. S. Army Engineer Research and Development Center (Vicksburg, MS) grant number W912HZ-04-2-0002, the Office of Naval Research grant number N00034-03-1-0116, the content of which does not necessarily reflect the position or policy of the government, and no official endorsement should be inferred. This work was also facilitated by use of the Network Visualization System for Computational Chemistry (NVSCC) (http://


  • Ab initio
  • Adsorption
  • Calcium oxide
  • Dimethyl methylphosphate
  • Trimethylphosphate


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