Substituents' effect in electron attachment to epigenetic modifications of cytosine

Epigenetic modifications of cytosine have been found to influence differently in many processes in biological systems. In order to investigate the differences in electron attachment to different epigenetic modifications of cytosine, we reported the A″ component of the integral cross section of electron scattering by cytosine (C) and its epigenetic modifications 5-methylcytosine (5mC), 5-hydroxymethylcytosine (5hmC), 5-formylcytosine (5fC), and 5-carboxylcytosine (5caC). Our results were obtained with the Schwinger multichannel method with pseudopotentials in the static-exchange (SE) and static-exchange plus polarization (SEP) approximations. In addition to the scattering results, we present electron attachment energies obtained through an empirical scaling relation for the five molecules. We observed three π^* resonances for C, 5mC, and 5hmC and four for 5fC and 5caC, in both SE and SEP approximations. The cross sections show that the π^* resonances of 5mC and 5hmC are located at higher energies than the resonances of C, while the resonances of 5fC and 5caC are located at lower energies. In order to investigate this shift in the resonances' positions, we analyzed the π^* lowest-lying orbitals and the electronic density over the molecules. Using the inductive and mesomeric effects, we were able to analyze the influence of each substituent over the molecule and on the resonances' positions.