Are charged tips driving TERS-resolution? A full quantum chemical approach

Experimental evidence suggests an extremely high, possibly even sub-molecular, spatial resolution of tip-enhanced Raman spectroscopy (TERS). While the underlying mechanism is currently still under discussion, two main contributions are considered: The involved plasmonic particles are able to highly confine light to small spatial regions in the near-field, i.e., the electromagnetic effect and the chemical effect due to altered molecular properties of the sample in close proximity to the plasmonic tip. Significant theoretical effort is put into the modeling of the electromagnetic contribution by various groups. In contrast, we previously introduced a computational protocol that allows for the investigation of the local chemical effect-including non-resonant, resonant, and charge transfer contributions-on a plasmonic hybrid system by mapping the sample molecule with a metallic tip model at the (time-dependent) density functional level of theory. In the present contribution, we evaluate the impact of static charges localized on the tip's frontmost atom, possibly induced by the tip geometry in the vicinity of the apex, on the TERS signal and the lateral resolution. To this aim, an immobilized molecule, i.e., tin(II) phthalocyanine (SnPc), is mapped by the plasmonic tip modeled by a single positively vs negatively charged silver atom. The performed quantum chemical simulations reveal a pronounced enhancement of the Raman intensity under non-resonant and resonant conditions with respect to the uncharged reference system, while the contribution of charge transfer phenomena and of locally excited states of SnPc is highly dependent on the tip's charge.