Modeling Raman Spectra in Complex Environments: From Solutions to Surface-Enhanced Raman Scattering

Abstract

This perspective highlights the essential physicochemical factors required for accurate computational modeling of Raman and Resonance Raman signals in complex environments. It highlights the theoretical challenges for obtaining a balanced quantum mechanical description of the molecular target, integration of target-environment interactions into the Hamiltonian, and explicit treatment of strong interactions such as hydrogen bonding. The dynamical sampling of solute–solvent phase space and the incorporation of plasmonic effects for Surface-Enhanced Raman Scattering (SERS) are also addressed. Through selected applications, we illustrate how these factors influence Raman signals and propose a framework to tackle these challenges effectively, advancing the reliability of theoretical Raman spectroscopy in real-world scenarios.