Abstract
Spatial interaction effects between charge carriers in ionic systems play a sizable role beyond a classical Maxwellian description. We develop a nonlocal, two-fluid, hydrodynamic theory of charges and study ionic plasmon effects, i.e. collective charge oscillations in electrolytes. Ionic spatial dispersion arises from both positive and negative charge dynamics with an impact in the (far-)infrared. Despite highly classical parameters, nonlocal quenching of up to 90% is observed for particle sizes spanning orders of magnitude. Notably, the ionic system is widely tunable via ion concentration, mass and charge, in contrast to solid metal nanoparticles. A nonlocal soft plasmonic theory for ions is relevant for biological and chemical systems bridging hard and soft matter theory and allowing the investigation of non-classical effects in electrolytes in full analogy to solid metal particles. The presented semi-classical approach allows studying plasmonic photo-catalysis introducing nonlocal aspects into electrolyte-metal interactions.
Highlights
The field of plasmonics is widely understood as the investigation of collective oscillations of the electron plasma in metallic systems induced by an external electromagnetic field
The question arises, if plasmon-like behavior can be observed in ionic systems and if interaction effects between the charge carriers play a sizable role as compared to the quantum effects observed for metal nanoparticles beyond a classical Maxwellian description[5,6,7,8,9]
Soft plasmonics for spherical ions[16] and chains of axons[15] have been studied within the RPA (Random Phase Approximation) method including Lorentz friction, i.e., electron radiation due to the acceleration of charges in the oscillations. Spatial dispersion phenomena such as charge (Coulomb) interaction and diffusion arise within the hydrodynamic model, where free charges are described within a linearized Navier-Stokes equation
Summary
The field of plasmonics is widely understood as the investigation of collective oscillations of the electron plasma in metallic systems induced by an external electromagnetic field. Soft plasmonics for spherical ions[16] and chains of axons[15] have been studied within the RPA (Random Phase Approximation) method including Lorentz friction, i.e., electron radiation due to the acceleration of charges in the oscillations. Spatial dispersion phenomena such as charge (Coulomb) interaction and diffusion arise within the hydrodynamic model, where free charges are described within a linearized Navier-Stokes equation. The semi-classical approach presented here can be fully integrated into standard nano-optic simulation frameworks and is considered to be of great interest for plasmonic photo-catalysis[44] introducing nonlocal aspects into electrolyte-metal interactions possibly avoiding the hardship of DFT calculations
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