Objectif The aim of this work is density functional based computation of thermodynamic and kinetic coefficients of redox reactions in solution, and relates these observable quantities to the electronic structure of electrochemical systems. Our computational tool is the ab initio molecular dynamics method. This method applies density functional theory (DFT) and molecular dynamics simulation techniques to make molecular model systems move under the influence of adiabatic forces obtained from a continuously updated electronic structure calculation. Unifying DFT and statistical mechanics at a fundamental level, this methodology has opened up the field of redox reactions in solution to first principle numerical study.The statistical mechanics of redox processes can be studied using suitable classical force field models. However, if the ultimate goal is quantitative comparison with the experiment, then the use of fairly high level electronic structure computation is absolutely mandatory, and of course, the electronic structure of solvation complexes is of interest itself, in particular, in the context of coordination chemistry. We will analyse the thermochemistry of simple redox half reactions in solution using the latest reliable path sampling methods, such as the transition sampling technique of the Chandler group or the Laio-Parrinello metadynamics. What we hope to achieve with this calculations is the beginning of a method for computational voltammetry and should enable us to measure reaction free energies, identify reaction coordinates (and in certain cases even probe kinetics) by scanning a range of values of the electrochemical potential. Combined with a transition state approach, this could ultimately yield information that can be used to understand current-voltage relations, bringing us a step closer to application ab initio MD methods to voltammetry. Champ scientifique sciences naturellessciences chimiquesélectrochimiesciences naturellessciences chimiqueschimie organiqueréaction organiquesciences naturellessciences chimiqueschimie physiquethermochimiesciences naturellessciences physiquesmécanique classiquemécanique statistique Mots‑clés Ab inito molecular dynamics DFT ionic solutions numerical simulations redox reactions in solution statistical mechanics Programme(s) FP6-MOBILITY - Human resources and Mobility in the specific programme for research, technological development and demonstration "Structuring the European Research Area" under the Sixth Framework Programme 2002-2006 Thème(s) MOBILITY-2.1 - Marie Curie Intra-European Fellowships (EIF) Appel à propositions FP6-2004-MOBILITY-5 Voir d’autres projets de cet appel Régime de financement EIF - Marie Curie actions-Intra-European Fellowships Coordinateur THE CHANCELLOR, MASTERS AND SCHOLARS OF THE UNIVERSITY OF CAMBRIDGE Adresse The old schools, trinity lane Cambridge Royaume-Uni Voir sur la carte Liens Site web Opens in new window Contribution de l’UE Aucune donnée
