Highlights with ‘Relativistic DFT’

Intramolecular 6-electron photo-redox reactions

Oxidative addition and reductive elimination reactions of small molecules possessing high-order bonds (e.g. N2, O2, NO+) is of fundamental interest in transition metal chemistry. As a means to study the mechanism and intermediates of such...

Relativistic and dispersion effects on O2 activation by metallic nanoparticles

In a recent study from KAUST, the effects of relativity and dispersion interactions were quantified for O2 adsorption and dissociation on Cu38, Ag38 and Au38 nanoparticles (NPs).The results indicate that the barrier for O2 dissociation almost...

Optical Properties of Silver and Gold Nanoparticles

In two recent papers, researchers from Trieste and Pisa studied the optical properties of silver and gold nanoparticles. The fundamental study on silver nanoshells showed that plasmonic features emerge at shells as small as 92 atoms....

Structural and electronic properties of uranium-encapsulated Au14

Gold nanoclusters have a good biocompatibility and low cytotoxicity. Encapsulated metal atoms can stabilize gold nanoclusters as well as change chemical and physical properties with respect to hollow clusters. Based on a typical Au14-cage structure, Prof. Wang...

Reactive cluster model of metallic glasses

Metallic glasses are still poorly understood, especially the lack of long-range order. In a bottom-up approach, researchers from the Colorado School of Mines have studied the chemical interactions between clusters underlying the acrystalline behavior of...

Catalytic oxygenation by Ruthenium Polyoxometalates

The catalytic oxydation of DMSO has been established with ruthenium polyoxometalates (POMs). The catalytic cycle has been revealed through a combination of experiments and theory, with the key intermediate established by relativistic DFT calculations as a POM-dimer...

Structure of gold-oxo nanoclusters in solution

The properties of the two know polyoxoaurates in [Au4As4O20]8– and  [Au4Se4O16]4– were recently studied in a combined experimental and theoretical effort. Through combining electrospray ionization mass spectrometry (ESI-MS) and UV/VIS spectroscopy and analysis with relativistic TDDFT calculations...

Closing the band gap in 2D semiconductors

Relativistic periodic DFT calculations show that the band gap of single-layer transition-metal dichalcogenides (MoWSeS) are reduced by high external electric fields. MoS2 and MoSe2 become metallic at fields of 6.5 V Å−1 and 4.5 V...

Uranyl nanocapsules: structure & stability

A combined experimental and theoretical exploration of uranyl nanoclusters is the recent cover piece of Chem. Eur. J.  Uranyl polyoxometalates from 28 units (U28) form nanocapsules that are stabilized by the anion they encapsulate. In this study...

Gold-Carbon Bonding in Gold-Alkynyl Complexes

Researchers from Brown University and Tsinghua University investigated and analyzed the chemical bonding between gold and carbon in gold-alkynyl complexes combining photoelectron spectroscopy and relativistic quantum chemical calculations. The importance of this work for understanding...