Publication

Ab initio molecular dynamics simulation of redox reactions of transition metal ions in aqueous solution and proteins

Ivano Tavernelli
2005
Conference Papers

Abstract

Redox potentials measure the free energy required to transfer a mol. species (ion) between two states of different total charge. In soln. a major contribution to the redox potential is the hydration free energy difference of the ion in the two oxidn. states which can in principle be computed from classical mol. dynamics (MD) simulation. However, for redox active transition metal ions reliable force fields are in general not available and one has to use quantum chem. methods which are capable of describing large solvent fluctuations. From this point of view Car-Parrinello MD (CPMD) combining 'on the fly' electronic structure calcn. with classical mol. dynamics of the ions is the method of choice for simulation of transition metal ions. In the last years we have been developing novel schemes for the computation of redox properties from first principles. In our approach reactant and product (i.e. the two oxidn. states of an ion) are described by two potential energy surfaces which differ by the no. of electrons. The transformation between the two surfaces can be enforced using geometrical constraints, thermodn. integration techniques or grand canonical methods. In addn. to redox potential the first two methods also yield free energy curves of oxidn. which can be used to test the predictions of Marcus theory of electron transfer. In the talk our computational methods will be explained and results presented for the half reactions Ag(I) -> Ag(II) and Ru(II) -> Ru(III) in aq. soln. and Ru(II) -> Ru(III) in a de-novo designed porphyrine-protein. [on SciFinder (R)]

Official source

https://infoscience.epfl.ch/entities/publication/499d0303-6aab-4f5a-9b8e-6e86ae227828

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Ivano Tavernelli
2005
Conference Papers

Abstract

Official source

https://infoscience.epfl.ch/entities/publication/499d0303-6aab-4f5a-9b8e-6e86ae227828

About this result

Related concepts (32)

Redox

Redox (ˈrɛdɒks , ˈriːdɒks , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a decrease in the oxidation state. There are two classes of redox reactions: Electron-transfer – Only one (usually) electron flows from the atom being oxidized to the atom that is reduced. This type of redox reaction is often discussed in terms of redox couples and electrode potentials.

Reduction potential

Redox potential (also known as oxidation / reduction potential, ORP, pe, , or ) is a measure of the tendency of a chemical species to acquire electrons from or lose electrons to an electrode and thereby be reduced or oxidised respectively. Redox potential is expressed in volts (V). Each species has its own intrinsic redox potential; for example, the more positive the reduction potential (reduction potential is more often used due to general formalism in electrochemistry), the greater the species' affinity for electrons and tendency to be reduced.

Standard electrode potential

In electrochemistry, standard electrode potential , or , is a measure of the reducing power of any element or compound. The IUPAC "Gold Book" defines it as: "the value of the standard emf (electromotive force) of a cell in which molecular hydrogen under standard pressure is oxidized to solvated protons at the left-hand electrode". The basis for an electrochemical cell, such as the galvanic cell, is always a redox reaction which can be broken down into two half-reactions: oxidation at anode (loss of electron) and reduction at cathode (gain of electron).

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