Atomistic QM/Classical Modeling of Surface-Enhanced Infrared Absorption

Abstract

We present a multiscale quantum mechanics/classical (QM/MM) approach for modeling surface-enhanced infrared absorption (SEIRA) spectra of molecules adsorbed on plasmonic nanostructures. The molecular subsystem is described at the density functional theory (DFT) level, while the plasmonic material is represented using fully atomistic, frequency-dependent Fluctuating Charges ($\omega$FQ) and Fluctuating Charges and Dipoles ($\omega$FQF$\mu$) models. These schemes enable an accurate and computationally efficient description of the plasmonic response of both graphene-based materials and noble metal nanostructures, achieving accuracy comparable to ab initio methods. The proposed methodology is applied to the calculation of SEIRA spectra of adenine adsorbed on gold nanoparticles and graphene sheets. The quality and robustness of the approach are assessed through comparison with surface-enhanced Raman scattering (SERS) spectra and available experimental data. The results demonstrate that the proposed framework provides a reliable route to simulate vibrational responses of plasmon-molecule hybrid systems.