Experimental and Computational Insights into the Overall Water Splitting Reaction by the Fe-Co-Ni-P Electrocatalyst.

Nonprecious transition-metal phosphides (TMPs) are versatile materials with tunable electronic and structural properties that could be promising as catalysts for energy conversion applications. Despite the facts, TMPs are not explored thoroughly to understand the chemistry behind their rich catalytic properties for the water splitting reaction. Herein, spiky ball-shaped monodispersed TMP nanoparticles composed of Fe, Co, and Ni are developed and used as efficient electrocatalysts for hydrogen and oxygen evolution reaction (HER, OER), and overall water splitting in alkaline medium; and their surface chemistry was explored to understand the reaction mechanism.

H NMR global diatropicity in copper hydride complexes.

Understanding the magnetic response of electrons in nanoclusters is essential to interpret their NMR spectra thereby providing guidelines for their synthesis towards various target applications. Here, we consider two copper hydride clusters that have applications in hydrogen storage and release under standard temperature and pressure. Through Born-Oppenheimer molecular dynamics simulations, we study dynamics effects and their contributions to the NMR peaks.

Cubic aromaticity in ligand-stabilized doped Au superatoms.

The magnetic response of valence electrons in doped gold-based M@AuL superatoms (M = Pd, Pt, Ag, Au, Cd, Hg, Ir, and Rh; L = PPh; and q = 0, +1, +2) is studied by calculating the gauge including magnetically induced currents (GIMIC) in the framework of the auxiliary density functional theory. The studied systems include 24 different combinations of the dopant, total cluster charge, and cluster structure (cubic-like or oblate). The magnetically induced currents (both diatropic and paratropic) are shown to be sensitive to the atomic structure of clusters, the number of superatomic electrons, and the chemical nature of the dopant metal.

Magnetically induced currents and aromaticity in ligand-stabilized Au and AuPt superatoms.

Understanding magnetically induced currents (MICs) in aromatic or metallic nanostructures is crucial for interpreting local magnetic shielding and NMR data. Direct measurements of the induced currents have been successful only in a few planar molecules but their indirect effects are seen in NMR shifts of probe nuclei. Here, we have implemented a numerically efficient method to calculate gauge-including MICs in the formalism of auxiliary density functional theory.

Solubility-Driven Isolation of a Metastable Nonagold Cluster with Body-Centered Cubic Structure.

The conventional synthetic methodology for atomically precise gold nanoclusters by using reduction in solution offers only the thermodynamically most stable nanoclusters. Herein, a solubility-driven isolation strategy is reported to access a metastable gold cluster. The cluster, with the composition of [Au (PPh ) ] (1), displays an unusual, nearly perfect body-centered cubic (bcc) structure.

Reassessment of the Four-Point Approach to the Electron-Transfer Marcus-Hush Theory.

The Marcus-Hush theory has been successfully applied to describe and predict the activation barriers and hence the electron-transfer (ET) rates in several physicochemical and biological systems. This theory assumes that in the ET reaction, the geometry of the free Gibbs energy landscape is parabolic, with equal curvature near the local minimum for both reactants and products. In spite of its achievements, more realistic models have included the assumption of the two parabolas having not the same curvature.

Theoretical Study of the Spin Competition in Small-Sized Al Clusters.

Stern-Gerlach (SG) experiments on aluminum clusters indicate that some small-sized aggregates exhibit a deflection signal consistent with the existence of magnetic moments. However, in the particular case of Al6 and Al8 clusters, electronic structure investigations show ambiguity on the 0 K ground spin state. In this work extensive computations of the electronic structure have been carried out in order to determine the ground state of these structures.