Abstract
The [RuCl6](4)(-)(aq) → [RuCl6](3)(-)(aq) + e(-) and [Ru(CN)6](4)(-)(aq) → [Ru(CN)6](3)(-)(aq) + e(-) half redox reactions are investigated using density functional based ab initio molecular dynamics methods. The aim is to understand at a microscopic level how the difference in π-bonding of these ligands is reflected in the redox chemistry. To this end, we have computed the redox and reorganization free energies using a method derived from the Marcus theory of electron transfer. The resulting estimate of the free energy change of the full redox reaction between the two coordination complexes is compared to experiment. Our findings indicate that ligand character has an important effect on the vertical ionization chemistry but less on the relaxation of the system after removal or addition of electrons. This enables us to correlate the redox free energies with the HOMO energy levels of the combined solute + solvent system and analyze the redox chemistry in terms of the corresponding energy level diagram.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
