QM/Classical Modeling of Surface Enhanced Raman Scattering Based on Atomistic Electromagnetic Models

We present quantum mechanics (QM)/frequency dependent fluctuating charge (QM/?FQ) and fluctuating dipoles (QM/?FQF?) multiscale approaches to model surface-enhanced Raman scattering spectra of molecular systems adsorbed on plasmonic nanostructures. The methods are based on a QM/classical partitioning of the system, where the plasmonic substrate is treated by means of the atomistic electromagnetic models ?FQ and ?FQF?, which are able to describe in a unique fashion and at the same level of accuracy the plasmonic properties of noble metal nanostructures and graphene-based materials. Such methods are based on classical physics, i.e. Drude conduction theory, classical electrodynamics, and atomistic polarizability to account for interband transitions, by also including an ad-hoc phenomenological correction to describe quantum tunneling. QM/?FQ and QM/?FQF? are thus applied to selected test cases, for which computed results are compared with available experiments, showing the robustness and reliability of both approaches. © 2023 The Authors. Published by American Chemical Society