Deciphering the direct heterometallic interaction in κ-bis(donor)ferrocenyl-transition-metal complexes.

Ligands featuring a 1,1'-bis(donor)ferrocene motif can adopt various binding modes. Among them, the κ binding mode, which involves interaction between the iron center of the ferrocene unit and the transition metal is the most unique. Although various examples highlight the interaction itself, the exact quantification of its strength remains uncertain.

Exploring the mechanism of graphene-oxide reduction by hydrazine in a multi-epoxide environment with DFT calculations.

Reduction mechanisms between hydrazine and a multi-epoxide arrangement were investigated on a finite-sized graphene-oxide model with density functional theory. Three multistep reaction pathways were explored to examine different graphene-oxide (GO) deoxygenation scenarios. Epoxides sharing the same hexagonal ring show the typical one-by-one elimination of the oxygen functional groups through two protonation steps and the formation of -diazine and water.

Computational modelling of ammonia addition on partially reduced graphene oxide flakes.

Density functional theory is employed to model the chemisorption of ammonia on epoxy-containing polycyclic aromatic hydrocarbons (PAHs) and understand the reaction mechanism of ammonia addition on partially reduced graphene oxide flakes. Coronene (CH) and ovalene (CH) based four-epoxy group containing molecules are used to mimic the RGO surface properties. The reaction mechanism changing effect of a second ammonia molecule as well as explicit water molecules is considered.

Ionic adsorption on the brucite (0001) surface: A periodic electrostatic embedded cluster method study.

Density functional theory (DFT) at the generalised gradient approximation level is employed within the periodic electrostatic embedded cluster method (PEECM) to model the brucite (0001) surface. Three representative studies are then used to demonstrate the reliability of the PEECM for the description of the interactions of various ionic species with the layered Mg(OH) structure, and its performance is compared with periodic DFT, an approach known to be challenging for the adsorption of charged species. The adsorption energies of a series of s block cations, including Sr and Cs which are known to coexist with brucite in nuclear waste storage ponds, are well described by the embedded cluster model, provided that basis sets of triple-zeta quality are employed for the adsorbates.

The importance of second shell effects in the simulation of hydrated Sr²⁺ hydroxide complexes.

Density functional theory at the meta-GGA level is employed to study the microsolvation of Sr(2+) hydroxides, in order to establish likely candidate species for the interaction of nuclear fission-generated strontium with corroded Magnox fuel cladding in high pH spent nuclear fuel storage ponds. A combination of the COSMO continuum solvation model and one or two shells of explicit water molecules is employed. Inclusion of only a single explicit solvation shell is unsatisfactory; open regions are present in the strontium coordination shell which would not exist in real aqueous complexes, and many optimised structures possess unavoidable energetic instabilities.