A hybrid-type approach with MD and DFT calculations for evaluation of redox potential of molecules

Abstract

A simple calculation method to evaluate the redox potential of molecules by using a hybrid-type calculation with molecular dynamics (MD) and density functional theory calculations is presented with discussions of the difference of the redox potential. In our hybrid method, the standard Gibbs free energy of the molecules, acetone and 3-pentanone, in the redox reaction, is estimated from the average of ionisation free energy and the excess chemical potentials of the reduced and oxidised molecules according to the Born–Haber cycle by sampled configurations from the MD simulation. The difference of the redox potentials between the two molecules is in agreement with the experimental data within the standard deviation.

Keywords::

• redox potential
• molecular dynamics
• Gibbs free energy
• density functional theory
• Born–Haber cycle

Disclosure statement

No potential conflict of interest was reported by the authors.

Additional information

Funding

This work was supported by a Grant-in-Aid for Young Scientists B [grant number 23750008] and a Grant-in-Aid for Exploratory Research [grant number 23655101].