A simplified density functional theory method for charged adsorbates on an ultrathin, insulating film supported by a metal substrate

Abstract

A simplified density functional theory (DFT) method for charged adsorbates on an ultrathin, insulating film supported by a metal substrate is developed and presented. This new method is based on a previous DFT development that uses a perfect conductor (PC) model to approximate the electrostatic response of the metal substrate, while the film and the adsorbate are both treated fully within DFT [I. Scivetti and M. Persson, Journal of Physics: Condensed Matter 25, 355006 (2013)]. The missing interactions between the metal substrate and the insulating film in the PC approximation are modelled by a simple force field (FF). The parameters of the PC model and the force field are obtained from DFT calculations of the film and the substrate, here shown explicitly for a NaCl bilayer supported by a Cu(100) surface. In order to obtain some of these parameters and the polarisability of the force field, we have to include an external, uniformly charged plane in the DFT calculations, which has required the development of a periodic DFT formalism to include such a charged plane in the presence of a metal substrate. This extension and implementation should be of more general interest and applicable to other challenging problems, for instance, in electrochemistry. As illustrated for the gold atom on the NaCl bilayer supported by a Cu(100) surface, our new DFT-PC-FF method allows us to handle different charge states of adsorbates in a controlled and accurate manner with a considerable reduction of the computational time. In addition, it is now possible to calculate vertical transition and reorganisation energies for charging and discharging of adsorbates that cannot be obtained by current DFT methodologies that include the metal substrate. We find that the computed vertical transition energy for charging of the gold adatom is in good agreement with experiments