Latest Publications

Journal of Computational Chemistry 2018

DOI: 10.1002/jcc.25148

A comprehensive theoretical study of the oxygen reduction reaction (ORR) over B,N‐codoped graphene has been carried out in the framework of DFT using two different approaches based on periodic or cluster models. The comparison and integration of the information provided by the two approaches allow achieving a more complete description of the studied phenomena, combining the advantages of both models. On one hand, the analysis of the structure, stability, and electronic properties of this catalyst permits to identify and characterize the active sites and provides insights into the origin of its high catalytic activity that should be found in the synergistic coupling of the opposite effects of the two B and N heteroatoms used as dopants. On the other hand, the study of the reaction mechanisms evidences that the process is thermodynamically favorable due to the overall high exothermicity, and that the 4e– transfer is the favorit...

The Journal of physical chemistry A 2018

DOI: 10.1021/acs.jpca.7b10033 pdf

To provide tools to interpret photochemical reactions, in this paper we demonstrate how a recently developed density-based index (DCT), up to now used in conjunction with time dependent density functional theory methods, can be extended to multiconfigurational methods. This index can guide chemists in the interpretation of photochemical reactions providing a measure of the spatial extent of a photoinduced charge transfer and, more generally, of charge transfer phenomena. This qualitative and quantitative description can be particularly relevant in the case of multiconfigurational calculations providing a simple tool for the interpretation of their complex outputs. To prove the potentiality of this approach we have considered a simple intramolecular excited state proton transfer reaction as study case and applied both wave function (CASSCF-CASPT2) and density-based methods in conjunction with a DCT analysis. Our re...

Chemistry European Journal 2018

DOI: 10.1002/chem.201704899 

Oxidative addition of iodoarenes (ArI) to Pd0 ligated by 1‐methyl‐1H‐imidazole (mim) in polar solvents leads to cationic arylpalladium(II) complexes [ArPd(mim)3]+. Kinetic analyses evidence that this reaction is second order with respect to the concentration of Pd0, and a mechanism involving the cooperative intervention of two Pd0 centers has been postulated to explain this finding. This unusual behavior is also observed with other nitrogen‐containing ligands and it is general for iodobenzenes substituted with electron‐donating or weakly electron‐withdrawing groups. In contrast, bromoarenes and electron‐poor iodoarenes display first‐order kinetics with respect to Pd0. Theoretical calculations performed at the density functional theory (DFT) level suggest the existence of mim‐ligated ArI‐Pd0 complexes, in which the iodoarene is bound to the metal in a halogen‐bond‐like fashion. Coordination weakens the C−I bond and facilitates t...

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