Extreme Electric Fields in DFT

Strong (10¹⁰ V/m) electric fields can be used to trigger chemical processes with extreme precision by selectively stabilizing or weakening bonds to initiate reactions which are otherwise slow or do not proceed at all. The ability to manipulate electric fields to tailor and stimulate bond-breaking events is a powerful experimental control knob, but one whose effects are difficult to predict due to a lack of suitable tools to probe its associated atomic-scale mechanisms. Here we introduce a novel approach, which we term the Generalized Dipole Correction (GDC), that enables the direct study of ultra-high fields effecting bond-breaking and desorption at the level of single atoms using Density Functional Theory (DFT). As a prototype application, we consider field evaporation from a kinked W (110) surface. We reveal two qualitatively different competing mechanisms that can be switched by the applied field.