Issue 7, 2016

A density functional theory protocol for the calculation of redox potentials of copper complexes

Abstract

A density functional theory (DFT) protocol for the calculation of redox potentials of copper complexes is developed based on 13 model copper complexes. The redox potentials are calculated in terms of Gibbs free energy change of the redox reaction at the theory level of CAM-B3LYP/6-31+G(d,p)/SMD, with the overall Gibbs free energy change being partitioned into the Gibbs free energy change of the gas phase reaction and the Gibbs free energy change of solvation. In addition, the calculated Gibbs free energy change of solvation is corrected by a unified correction factor of −0.258 eV as the second-layer Gibbs free energy change of solvation and other interactions for each redox reaction. And an empirical Gibbs free energy change of solvation at −0.348 eV is applied to each water molecule if the number of inner-sphere water molecule changes during the redox reaction. Satisfactory agreements between the DFT calculated and experimental results are obtained, with a maximum absolute error at 0.197 V, a mean absolute error at 0.114 V and a standard deviation at 0.133 V. Finally, it is concluded that the accurate prediction of redox potentials is dependent on the accurate prediction of geometrical structures as well as on geometrical conservation during the redox reaction.

Graphical abstract: A density functional theory protocol for the calculation of redox potentials of copper complexes

Supplementary files

Article information

Article type
Paper
Submitted
01 Nov 2015
Accepted
05 Jan 2016
First published
07 Jan 2016

Phys. Chem. Chem. Phys., 2016,18, 5529-5536

A density functional theory protocol for the calculation of redox potentials of copper complexes

L. Yan, Y. Lu and X. Li, Phys. Chem. Chem. Phys., 2016, 18, 5529 DOI: 10.1039/C5CP06638G

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements