Significant bonding rearrangements triggered by Mg4 clusters

Abstract

Among new nanostructures with exciting reactivity features, Mg4 clusters present a promising catalytic behavior. The structure, stability and bonding of the complexes formed by the interaction of Mg4 clusters and first row Lewis bases, namely ammonia, water and hydrogen fluoride, have been investigated through the use of high-level G4 single-reference and CASPT2 multireference formalisms. The adducts formed reflect the high electrophilicity of the Mg4 cluster through holes in the neighborhood of each metallic center. After the adducts formation, the metallic bonding of the Mg4 moiety is not significantly altered so the hydrogen shifts from the Lewis base toward the Mg atoms lead to new local minima with enhanced stability. For the particular case of ammonia and water, the global minima obtained when all the hydrogens of the Lewis base are shifted to the Mg4 moiety have in common a very stable scaffold with a N or O center covalently tetracoordinated to the four Mg atoms, so the initial bonding arrangements of both reactants have completely disappeared.

Investigating the catalytic activity of Mgn (n = 4–8) clusters for the hydrogen evolution reaction using density functional theory

“…The reactants were studied, and each tip on the IRI 2D graphic represent the formation of bonds. The Mg 4 cluster on the IRI 3D graphic agree with the research findings, which proves that the Mg 4 cluster and H 2 O adsorb chemically in fact [51]. When sing(λ 2 )ρ<0, the density of the scatters show the strength of the interaction, and the denser the scatters, the stronger the week interaction.…”

Hydrogen evolution reaction of Ben + H2O (n = 5–9) based on density functional theory

“…22–27 Vos et al . 28,29 reported a high level of single-reference and multi-reference ab initio calculations showing that Be 4 clusters exhibit very efficient Lewis acids when interacting with conventional Lewis bases such as ammonia, water, or hydrogen fluoride. The corresponding acid–base interactions trigger the sequential dissociation of all Lewis bases.…”

“…As doped, Be atoms effectively improve the NLO reaction, thermodynamics, and hydrogen adsorption properties of Al 12 N 12 nanoclusters, which were found in the study of Mehboob et al 21 Recent studies on two-dimensional structures, clusters and visible-light-driven photocatalytic hydrogen evolution reactions are also effective methods for developing hydrogen energy. [22][23][24][25][26][27] Vos et al 28,29 reported a high level of single-reference and multireference ab initio calculations showing that Be 4 clusters exhibit very efficient Lewis acids when interacting with conventional Lewis bases such as ammonia, water, or hydrogen fluoride. The corresponding acid-base interactions trigger the sequential dissociation of all Lewis bases.…”