Nature of Charge Transfer Effects in Complexes of Dopamine Derivatives Adsorbed on Graphene-Type Nanostructures

Continuing the investigation started for dopamine (DA) and dopamine-o-quinone (DoQ) (see , the light absorption and charge transfer properties of the dopamine zwitterion (called dopamine-semiquinone or DsQ) adsorbed on the graphene nanoparticle surface is investigated using the ground state and linear-response time-dependent density functional theories, considering the B97X-D3BJ/def2-TZVPP level of theory. In terms of the strength of molecular adsorption on the surface, the DsQ form has 50% higher binding energy than that found in our previous work for the DA or DoQ cases (−20.24 kcal/mol vs. −30.41 kcal/mol). The results obtained for electronically excited states and UV-Vis absorption spectra show that the photochemical behavior of DsQ is more similar to DA than that observed for DoQ. Of the three systems analyzed, the DsQ-based complex shows the most active charge transfer (CT) phenomenon, both in terms of the number of CT-like states and the amount of charge transferred. Of the first thirty electronically excited states computed for the DsQ case, eleven are purely of the CT type, and nine are mixed CT and localized (or Frenkel) excitations. By varying the adsorption distance between the molecule and the surface vertically, the amount of charge transfer obtained for DA decreases significantly as the distance increases: for DoQ it remains stable, for DsQ there are states for which little change is observed, and for others, there is a significant change. Furthermore, the mechanistic compilation of the electron orbital diagrams of the individual components cannot describe in detail the nature of the excitations inside the complex.