Shape Plasmonics and Geometric Eigenvalues: The Crystal Field Plasmon Splitting in a Sphere-to-Cube Continuous Transition

TL;DR

This paper investigates how the shape transition from sphere to cube in gold nanoparticles affects plasmonic resonances, introducing a novel electromagnetic analogy to crystal field splitting to explain eigenvalue variations.

Contribution

It introduces a minimal model based on crystal field theory to explain shape-dependent plasmonic eigenvalues and wavelengths in nanoparticles, bridging electromagnetic and solid-state concepts.

Findings

Eigenvalues follow a Tanabe-Sugano diagram pattern.

The model accurately predicts experimental and simulated plasmon wavelengths.

Shape influences plasmonic modes through topological and charge defect effects.

Abstract

A smooth sphere-to-cube transition is experimentally, computationally and theoretically studied in plasmonic Au nanoparticles, including retardation effects. Localized surface plasmon-polariton resonances were described with precision, discriminating among the influences of shape statistics, particle polydispersity, electrochemistry of excess (surface) charges. Sphere, cube and semicubes in between all show well-defined secular electrostatic eigenvalues, producing a wealthy of topological modes afterwards quenched by charge relaxation processes. The way both eigenvalues and plasmon wavelength vary as a function of a shape descriptor, parametrizing the transition, is explained by a minimal model based on the key concepts of crystal (or ligand) field theory (CFT), bringing for the first time to an {\em electromagnetic analog of crystal field splitting}. For any orbital angular momentum, eigenvalues evolve as in a Tanabe-Sugano correlation diagram, relying on the symmetry set by particle topology and a charge defect between cube and sphere. Expressions for non-retarded and retarded plasmon wavelengths are given and succeffully applied to both experimental UV-Vis and numerically simulated values. The CFT analogy can be promising to delve into the role of shape in nanoplasmonics and nanophotonics.