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Building onto a recent serious of ab initio studies of various acid-gas reactions with metal oxide sorbents, electronic structure methods are being used to study the addition of CS₂ to Group IV (MO₂)ₙ and Group VI (MO₃)ₙ (n = 1, 2, 3) nanoclusters, beginning with the MO₂ and MO₃ monomers according to a “bottom-up” approach. The preliminary density functional theory (DFT) calculations in this study provide structures and vibrational frequency thermodynamic corrections for later expanding upon by way of single point correlated molecular-orbital theory (MO) calculations, mainly CCSD(T) and MP2 to study the structures and energies which could arise from Lewis acid-base addition (physisorption) and formation of COS₂²⁻ (chemisorption) of CS₂ to these clusters will be predicted. For future work, these CS₂ ligand binding energies (LBE) will be compared to established CO₂ results in the literature and to any known experimental and computational values for the interactions of CS₂ with bulk metal oxides. These LBEs will then be analyzed for any correlation to any known trends in the metal oxide Lewis acidity, metal oxide redox chemistry, and acid gas basicity to establish useful thermodynamic benchmarks for the practicality of Group IV and Group VI transition metal oxides for the sequestration and conversion of CS₂. The results of this work and beyond could also have serious implications for the sequestration of CS₂ from high-sulfur areas of the arctic permafrost and could provide valuable mechanistic insights into the possible reactions and products of metal oxide degradation during the Claus Process.

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Predicting the Reactions of CS2 with Group IV and Group VI Transition Metal Oxides



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