Highlights with ‘Reactivity’

Intersystem crossing through spin-orbit coupling in Os(II) complexes

The Os(fipz)(tfa)(CO)3 (tfa = trifluoroacetate, fipz=3-trifluoromethyl-5-(1-isoquinolinyl)-1,2-pyrazole) complex shows excitation-dependent emission quantum yield. The higher-energy excitation (< 340 nm) contributes more to phosphorescence than fluorescence, implying stronger intersystem crossing (ISC) for highly excited singlet states. Theoretical...

ReaxFF molecular dynamics simulations on lithium sulfur batteries

Understanding of the structural, and kinetic behavior of the sulfur cathode materials are crucial for designing high performance Li-S batteries. In a recent study, ReaxFF molecular dynamics simulations has been utilized to study sulfur cathode...

Insights into the components of MAO mixtures

Methylaluminoxane (MAO) is one of the most commonly utilized co-catalysts in the single-site production of polyolefins catalyzed by metallocenes. However, its exact structure has eluded experimental characterization because of the dynamic equilibrium between various species...

ReaxFF: Teflon coating reduces Li-S battery electrolyte decomposition

Lithium released from the anode is a highly exothermic process in lithium-sulfur batteries, and as such can lead to reactions with the electrolyte. In a recent ReaxFF study, the lithium discharge from a single-walled carbon...

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...

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...

Multi-scale Modeling of Chemistry in Water

Accurate modeling of chemical reactions in realistic aqueous environments calls for an efficient multi-scale quantum mechanical/molecular mechanical (QM/MM) approach. However, since solvent molecules diffuse in and out of the region of interest, new adaptive approaches...

Insights in Mo (di)hydride bonds with ETS-NOCV

Bonding interactions in non-classical hydride/dihydrogen molybdocenes and their interconversion to trihydrides have been analyzed with ETS-NOCV in a recent inside-cover featured article. Ansa-bridges with a small bite angle make the Mo center more sterically available, favoring the...

Slaters beat Gaussians for Fe-complexes

In a recent paper, J. Phys. Chem. A, 112 (28), p. 6384, 2008, Güell, Luis, Sola, and Swart, compare ADF’s Slater Type Orbital (STO) basis sets to Gaussian Type Orbitals (GTO) basis sets in a...

Modeling Ditopic ion-pair receptors with ADF and QUILD

While nucleobase quartets are known today for all natural nucleobases and combinations of these, no reports of anion-binding properties of natural nucleobase quartets are known. In a recent communication, Tushar van der Wijst, Célia Fonseca...