Computation of Oxidation Potentials of Solvated Nucleobases by Static and Dynamic Multilayer Approaches

The determination of the redox properties of nudeobases is of paramount importance to get insight into the charge-transfer processes in which they are involved, such as those occurring in DNA-inspired biosensors. Although many theoretical and experimental studies have been conducted, the value of the one-electron oxidation potentials of nudeobases is not well-defined. Moreover, the most appropriate theoretical protocol to model the redox properties has not been established yet. In this work, we have implemented and evaluated different static and dynamic approaches to compute the one-electron oxidation potentials of solvated nucleobases. In the static framework, two thermodynamic cydes have been tested to assess their accuracy against the direct determination of oxidation potentials from the adiabatic ionization energies. Then, the introduction of vibrational sampling, the effect of implicit and explicit solvation models, and the application of the Marcus theory have been analyzed through dynamic methods. The results revealed that the static direct determination provides more accurate results than thermodynamic cycles. Moreover, the effect of sampling has not shown to be relevant, and the results are improved within the dynamic framework when the Marcus theory is applied, especially in explicit solvent, with respect to the direct approach. Finally, the presence of different tautomers in water does not affect significantly the one-electron oxidation potentials.

Automated summary

The determination of the redox properties of nucleobases is essential for understanding the charge-transfer processes in DNA-inspired biosensors. This study implemented and evaluated different static and dynamic approaches to compute the one-electron oxidation potentials of solvated nucleobases. The results showed that the static direct determination method provided more accurate results than thermodynamic cycles, and the application of the Marcus theory improved the results within the dynamic framework.