Cluster Quantum Chemical Study of the Interaction of Dimethyl Methylphosphonate with Magnesium Oxide

Zhanpeisov, Nurbosyn U.; Zhidomirov, G. M.; Yudanov, Ilya V.; Klabunde, Kenneth J.

doi:10.1021/j100091a015

Cited by 37 publications

(37 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Moreover, this situation is similar as it was found in the case of Tabun adsorbed on small models of CaO [30] where the target molecule also forms a chemical bond with the nonhydroxylated CaO surface. It is also in agreement with the results of the theoretical study of DMMP adsorption on MgO [28] where the one-center molecular adsorption was found to be more favorable. The A2-DMMP complex is additionally stabilized by the formation of two hydrogen bonds of the C-HÁÁÁO type in which the Oa and Ob atoms of the surface are involved as proton-acceptors and the molecular C1-H and C2-H groups are proton-donors.…”

Section: Nature Of Interactions Between Dmmp and The Model Cao Surfacessupporting

confidence: 90%

“…It has been shown that aluminum, magnesium, and lanthanum oxides behave in a similar way, with initial binding of the P=O species to the surface, followed by stepwise elimination of the methoxy groups, combined with surface hydrogen to form methanol [4]. Cluster quantum-chemical study of destructive adsorption of DMMP [28] and sarin [29] on magnesium oxide surface and a theoretical work of adsorption of tabun on calcium oxide cluster models [30] were published.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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

2008

View full text Add to dashboard Cite

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 Ca 4 O 4 , completely hydroxylated Ca 4 O 4 (OH) 2 H 2 , and partially hydroxylated Ca 4 O 4 (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).

show abstract

Section: Nature Of Interactions Between Dmmp and The Model Cao Surfacessupporting

confidence: 90%

Section: Introductionmentioning

confidence: 99%

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

2008

View full text Add to dashboard Cite

show abstract

“…Also, the finding of strong interactions between Sarin and the MgO surface in the first step of decomposition 48 is consistent with the results of experimental studies 27,28 and a quantum chemical study. 67 Our optimized geometries of conformers are in good agreement with these findings and relevant for the study of DMPT decomposition. The adsorption energy values (Table 2) indicate that Models A and B are more stable compared to Models C and D. The enhanced stability in Model A (adsorption via O1, P, and O2 atoms) and Model B Fig.…”

Section: Resultssupporting

confidence: 85%

“…Conformational search with different initial positions of DMPT reveals that it could be adsorbed on the Mg 4 O 4 surface in four different ways due to the formation of chemical bonds between the P, O1, O2 (Model A), or P, O1, S (Model B) or P, O1 (Model C) or only the O1 (Model D) and the MgO surface. 67 Our optimized geometries of conformers are in good agreement with these findings and relevant for the study of DMPT decomposition. 2, while the adsorption energies are collected in Table 2.…”

Section: Adsorption Of Dmpt On Mg 4 O 4 and Mg 4 O 4 (Oh) 2 Hsupporting

confidence: 85%

Decomposition of O,S-dimethyl methylphosphonothiolate by ammonia on magnesium oxide: a theoretical study of catalytic detoxification of a chemical warfare agent

Sahu

Ghosh

Sen

et al. 2015

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

The adsorption of a model nerve agent, O,S-dimethyl methylphosphonothiolate (DMPT), on the hydroxylated and unhydroxylated nano-crystalline magnesium oxide surface followed by the nucleophilic attack of ammonia (NH3) is investigated at the M06-2X/6-311++G(d,p) level of theory using the representative cluster models. The geometries of DMPT and NH3 are fully optimized, while the geometry of the oxide fragment is kept frozen. The main insight of this study is the incorporation of the Eley-Rideal mechanism for the first time in the detoxification process, where one of the reactant molecules (DMPT) is adsorbed and the other one (NH3) reacts with it directly impinging from the gas phase. There are two possible pathways of nucleophilic detoxification, either concerted or stepwise. The nature of the first transition state of nucleophilic attack in both pathways is the vital step for degradation. Our calculated results predict that the reaction of DMPT with NH3 gives rise to both P-S and P-O bond cleavage completely. Also, the P-S cleavage is found to be the favorable one over P-O bond breaking. The exploration of the overall reaction mechanism has established the catalytic activity of nano-crystalline MgO in nucleophilic DMPT degradation, as in all cases the activation barriers have reduced compared to the previously reported aminolysis of DMPT in the gas phase. Interestingly, the hydroxylated model has better catalytic performance than the unhydroxylated one.

show abstract

“…In turn, theory can predict properties of real CWAs. Quantum chemical calculations have been employed recently mainly to explore gas-phase decomposition mechanisms of DMMP 4,5 and to simulate adsorption and decomposition of DMMP and real agents (Sarin and VX) on various oxides, [6][7][8][9][10][11] carbon nanotubes, 12 and graphene. 13 The electronic structure of DMMP is also interesting from a basic spectroscopy perspective.…”

Section: Introductionmentioning

confidence: 99%

Electron Spectroscopy and Computational Studies of Dimethyl Methylphosphonate

Head

Tsyshevsky²,

Trotochaud

et al. 2016

J. Phys. Chem. A

View full text Add to dashboard Cite

Dimethyl methylphosphonate (DMMP) is one of the most widely used molecules to simulate chemical warfare agents in adsorption experiments. However, the details of the electronic structure of the isolated molecule have not yet been reported. We have directly probed the occupied valence and core levels using gas phase photoelectron spectroscopy and the unoccupied states using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Density functional theory (DFT) calculations were used to study the electronic structure, assign the spectral features, and visualize the molecular orbitals. Comparison with parent molecules shows that valence and core-level binding energies of DMMP follow trends of functional group substitution on the P center. The photoelectron and NEXAFS spectra of the isolated molecule will serve as a reference in studies of DMMP adsorbed on surfaces.

show abstract

Cluster Quantum Chemical Study of the Interaction of Dimethyl Methylphosphonate with Magnesium Oxide

Cited by 37 publications

References 0 publications

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

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

Decomposition of O,S-dimethyl methylphosphonothiolate by ammonia on magnesium oxide: a theoretical study of catalytic detoxification of a chemical warfare agent

Electron Spectroscopy and Computational Studies of Dimethyl Methylphosphonate

Contact Info

Product

Resources

About