Structural Reconstruction of a Cobalt- and Ferrocene-Based Metal-Organic Framework during the Electrochemical Oxygen Evolution Reaction.

Metal-organic frameworks (MOFs) are increasingly being investigated as electrocatalysts for the oxygen evolution reaction (OER) due to their unique modular structures that present a hybrid between molecular and heterogeneous catalysts, featuring well-defined active sites. However, many fundamental questions remain open regarding the electrochemical stability of MOFs, structural reconstruction of coordination sites, and the role of formed species. Here, we report the structural transformation of a surface-grown MOF containing cobalt nodes and 1,1'-ferrocenedicarboxylic acid linkers (denoted as CoFc-MOF) during the OER in alkaline electrolyte.

Excited-State Properties for Extended Systems: Efficient Hybrid Density Functional Methods.

Time-dependent density functional theory has become state-of-the-art for describing photophysical and photochemical processes in extended materials because of its affordable cost. The inclusion of exact exchange was shown to be essential for the correct description of the long-range asymptotics of electronic interactions and thus a well-balanced description of valence, Rydberg, and charge-transfer excitations. Several approaches for an efficient treatment of exact exchange have been established for the ground state, while implementations for excited-state properties are rare.

The Role of Cation-Vacancies for the Electronic and Optical Properties of Aluminosilicate Imogolite Nanotubes: A Non-local, Linear-Response TDDFT Study.

We report a combined non-local (PBE-TC-LRC) Density Functional Theory (DFT) and linear-response time-dependent DFT (LR-TDDFT) study of the structural, electronic, and optical properties of the cation-vacancy based defects in aluminosilicate (AlSi) imogolite nanotubes (Imo-NTs) that have been recently proposed on the basis of Nuclear Magnetic Resonance (NMR) experiments. Following numerical determination of the smallest AlSi Imo-NT model capable of accommodating the defect-induced relaxation with negligible finite-size errors, we analyse the defect-induced structural deformations in the NTs and ensuing changes in the NTs' electronic structure. The NMR-derived defects are found to introduce both shallow and deep occupied states in the pristine NTs' band gap (BG).

First principles calculations of optical properties for oxygen vacancies in binary metal oxides.

Using an advanced computational methodology implemented in CP2K, a non-local PBE0-TC-LRC density functional and the recently implemented linear response formulation of the Time-dependent Density Functional Theory equations, we test the interpretation of the optical absorption and photoluminescence signatures attributed by previous experimental and theoretical studies to O-vacancies in two widely used oxides-cubic MgO and monoclinic (m)-HfO. The results obtained in large periodic cells including up to 1000 atoms emphasize the importance of accurate predictions of defect-induced lattice distortions. They confirm that optical transitions of O-vacancies in 0, +1, and +2 charge states in MgO all have energies close to 5 eV.

Micrometre-long covalent organic fibres by photoinitiated chain-growth radical polymerization on an alkali-halide surface.

On-surface polymerization is a promising technique to prepare organic functional nanomaterials that are challenging to synthesize in solution, but it is typically used on metal substrates, which play a catalytic role. Previous examples on insulating surfaces have involved intermediate self-assembled structures, which face high barriers to diffusion, or annealing to higher temperatures, which generally causes rapid dewetting and desorption of the monomers. Here we report the photoinitiated radical polymerization, initiated from a two-dimensional gas phase, of a dimaleimide monomer on an insulating KCl surface.

Efficient parametrization of complex molecule-surface force fields.

We present an efficient scheme for parametrizing complex molecule-surface force fields from ab initio data. The cost of producing a sufficient fitting library is mitigated using a 2D periodic embedded slab model made possible by the quantum mechanics/molecular mechanics scheme in CP2K. These results were then used in conjunction with genetic algorithm (GA) methods to optimize the large parameter sets needed to describe such systems.

Hydrogen-induced rupture of strained Si─O bonds in amorphous silicon dioxide.

Using ab initio modeling we demonstrate that H atoms can break strained Si─O bonds in continuous amorphous silicon dioxide (a-SiO(2)) networks, resulting in a new defect consisting of a threefold-coordinated Si atom with an unpaired electron facing a hydroxyl group, adding to the density of dangling bond defects, such as E' centers. The energy barriers to form this defect from interstitial H atoms range between 0.5 and 1.

Using metallic noncontact atomic force microscope tips for imaging insulators and polar molecules: tip characterization and imaging mechanisms.

We demonstrate that using metallic tips for noncontact atomic force microscopy (NC-AFM) imaging at relatively large (>0.5 nm) tip-surface separations provides a reliable method for studying molecules on insulating surfaces with chemical resolution and greatly reduces the complexity of interpreting experimental data. The experimental NC-AFM imaging and theoretical simulations were carried out for the NiO(001) surface as well as adsorbed CO and Co-Salen molecules using Cr-coated Si tips.

Effects of atomic scale roughness at metal/insulator interfaces on metal work function.

We evaluate the performance of different van der Waals (vdW) corrected density functional theory (DFT) methods in predicting the structure of perfect interfaces between the LiF(001), MgO(001), NiO(001) films on the Ag(001) surface and the resulting work function shift of Ag(001). The results demonstrate that including the van der Waals interaction is important for obtaining accurate interface structures and the metal work function shift. The work function shift results from a subtle interplay of several effects strongly affected by even small changes in the interface geometry.