Transient negative ion spectrum of the cytosine-guanine pair

Abstract

We employed elastic scattering calculations, performed in the static exchange approximation, to investigate the π ∗ transient anion states of cytosine, guanine and the cytosine-guanine pair. Our results for the isolated monomers, also obtained in the static-exchange plus polarization approximation, are in good agreement with the available calculations and electron transmission data. Virtual orbital analysis for the lower-lying π ∗ anion states, with pure shape resonance character, indicates that electron attachment to the cytosine-guanine pair gives rise to resonances located on either monomer (the orbitals do not delocalize over the pair). The π ∗ shape resonances of the pair localized on the cytosine unit have lower energies in comparison with those of the isolated base, with the opposite trend for the guanine unit. The underlying mechanism would be the net positive charge transfer to the cytosine unit, as the guanine monomer acts as a proton donor in two out of the three hydrogen bonds formed in the pair. Even though the calculations were performed in the static-exchange approximation (due to the size of the system), the conclusions drawn were also corroborated by empirical estimates of the vertical attachment energies. The results for the cytosine-guanine pair are compared to those previously obtained for the formic acid-formamide complex, having two hydrogen bonds with opposite donor/acceptor characters and negligible charge transfer.