Quantum corrections in nanoplasmonics: shape, scale, and material

The classical treatment of plasmonics is insufficient at the nanometer-scale due to quantum mechanical surface phenomena. Here, an extension to the classical paradigm is reported which rigorously remedies this deficiency through the incorporation of first-principles surface response functions - the Feibelman d-parameters - in general geometries. Several analytical results for the leading-order plasmonic quantum corrections are obtained in a first-principles setting; particularly, a clear separation of the roles of shape, scale, and material is established. The utility of the formalism is illustrated by the derivation of a modified sum-rule for complementary structures, a rigorous reformulation of Kreibig's phenomenological damping prescription, and an account of the small-scale resonance-shifting of simple and noble metal nanostructures. These insights open the technological design space and deepen our fundamental understanding of nanoplasmonics beyond the classical regime.