Quantum Chemical Study of the Reactions between Pd⁺/Pt⁺ and H₂O/H₂S

Abstract

The study of the reactions of water and hydrogen sulfide with palladium and platinum cations has been completed in this work, in both low- and high-spin states. Our calculations predict that only the formation of platinum sulfide is exothermic (in both spin states), whereas for the remaining species the oxides and sulfides are found to be more reactive than their corresponding bare metal cations. An in-depth analysis of the reaction paths leading to metal oxide and sulfide species is given, including various minima, and several important transition states. All results have been compared with existing experimental and theoretical data, and earlier works covering the reaction of nickel cation with water and hydrogen sulfide to observe the trends for the group 10 transition metals.

Chemical Reactivity Studies by the Natural-Orbital-Functional 2nd-Order-Moller-Plesset (NOF-MP2) method. Water Dehydrogenation by the Scandium Cation

“…The large and increasing number of combined theoretical/experimental chemical reaction mechanistic studies, indisputably shows that the development of reliable and computationally efficient density functional theory (DFT) based methods has contributed greatly to this present status [2]. In this vein, the reactions of transition metal cations with a large variety of substrates, including both first-and second-row hydrides [3][4][5][6][7][8] and, in particular water [9][10][11][12][13], have been exhaustively studied. Thus, the studies alluded to above have firmly established that the earlier transition metal cations (Sc + , Ti + , V + , Cr + and Mn + ) are more reactive than their corresponding oxides, while the opposite is true for the late transition metal cations (Co + , Ni + and Cu + ).…”