How covalence breaks adsorption-energy scaling relations and solvation restores them† †Electronic supplementary information (ESI) available: Assessment of adsorption energies, models used for the oxygen evolution and reduction reactions, details of the calculations in ADF, tables with spin states, zero-point energies, solvation energies, adsorption energies and ligand effects. See DOI: 10.1039/c6sc02123a Click here for additional data file.

How covalence breaks adsorption-energy scaling relations and solvation restores them.

It is known that breaking the scaling relations between the adsorption energies of *O, *OH, and *OOH is paramount in catalyzing more efficiently the reduction of O2 in fuel cells and its evolution in electrolyzers. Taking metalloporphyrins as a case study, we evaluate here the adsorption energies of those adsorbates on the metal centers Cr, Mn, Fe, Co, Ni and Cu, using H, F, OH, NH2, CH3, and B...

Why conclusions from platinum model surfaces do not necessarily lead to enhanced nanoparticle catalysts for the oxygen reduction reaction† †Electronic supplementary information (ESI) available: Data in Fig. 1 and 3, details of the electrochemical setup and measurements, method to assess the experimental *OH adsorption energies, theoretical details of the ORR modeling, assessment of free energies and generalized coordination numbers, schematics of reconstructed Pt(110) active sites on Pt201 and Pt368, zoom in Fig. 3's concave region. See DOI: 10.1039/c6sc04788b Click here for additional data file.

1 Leiden Institute of Chemistry, Leiden University, PO Box 9502, 2300 RA Leiden, The Netherlands. 2 Physik-Department ECS,Technische Universität München, James-Franck-Str. 1, D-85748 Garching, Germany. 3 Univ Lyon, Ens de Lyon, CNRS UMR 5182, Université Claude Bernard Lyon 1, Laboratoire de Chimie, F-69342, Lyon, France. 4 Department of Chemical and Biomolecular engineering, University of Calif...

Real single ion solvation free energies with quantum mechanical simulation† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc02138k Click here for additional data file.

Single ion solvation free energies are one of the most important properties of electrolyte solutions and yet there is ongoing debate about what these values are. Only the values for neutral ion pairs are known. Here, we use DFT interaction potentials with molecular dynamics simulation (DFT-MD) combined with a modified version of the quasi-chemical theory (QCT) to calculate these energies for th...

Structure and spin state of nonheme FeIVO complexes depending on temperature: predictive insights from DFT calculations and experiments† †Electronic supplementary information (ESI) available: Methods section, Tables S1–S8, all the data for DFT calculations (Tables S9–S53 for energies, Mulliken spin density distribution, and selected geometries), and coordinates. See DOI: 10.1039/c7sc01738c Click here for additional data file.

Near-IR absorbing donor–acceptor ligand-to-ligand charge-transfer complexes of nickel(ii)† †Electronic supplementary information (ESI) available: Complete experimental procedures, 1H, 13C and VT NMR data, complete electrochemical and solvatochromic analysis, and frontier orbital energies and atomic positions from DFT calculations. CCDC 1414822–1414824. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc02703a Click here for additional data file. Click here for additional data file.