Mixed Atomistic-Implicit Quantum/Classical Approach to Molecular Nanoplasmonics

Abstract: A multiscale QM/classical approach is presented, that is able to model the optical properties of complex nanostructures composed of a molecular system adsorbed on metal nanoparticles. The latter are described by a combined atomistic-continuum model, where the core is described using the implicit boundary element method (BEM) and the surface retains a fully atomistic picture and is treated employing the frequency-dependent fluctuating charge and fluctuating dipole ($\omega$FQF$\mu$) approach. The integrated QM/$\omega$FQF$\mu$-BEM model is numerically compared with state-of-the-art fully atomistic approaches, and the quality of the continuum/core partition is evaluated. The method is then extended to compute Surface-Enhanced Raman Scattering (SERS) within a Time-Dependent Density Functional Theory (TDDFT) framework.