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Tip-enhanced Raman spectroscopy (TERS) is a valuable method for surfaceanalysis with nanometer to angstrom-scale resolution, however, the accuratesimulation of particular TERS signals remains a computational challenge. Wepresent a unique approach to this challenge by combining the two maincontributors to plasmon-enhanced Raman spectroscopy and to the high resolutionin TERS in particular, the electromagnetic and the chemical effect, into onequantum mechanical simulation. The electromagnetic effect describes thesample's interaction with the strong, highly localized and inhomogeneouselectric fields associated with the plasmonic tip, and is typically thethematic focus for most mechanistic studies. On the other hand, the chemicaleffect covers the different responses to the extremely close-range and highlyposition-sensitive chemical interaction between the apex tip atom(s) and thesample, and, as we could show in previous works, plays an often underestimatedrole. Starting from a (time-dependent) density functional theory description ofthe chemical model system, comprised of a tin(II) phthalocyanine (SnPc) samplemolecule and a single silver atom as tip, we introduce the electromagneticeffect through a series of point charges that recreate the electric field inthe vicinity of the plasmonic Ag nanoparticle. By scanning the tip over themolecule along a 3D grid, we can investigate the system's Raman response oneach position for non-resonant and resonant illumination. Simulating botheffects on their own already hints at the achievable signal enhancement andresolution, but the combination of both creates even stronger evidence thatTERS is capable of resolving sub-molecular features.

A full quantum mechanical approach assessing the chemical and electromagnetic effect in TERS