arXiv subjects

Xabier Arrieta

Publications and source records attributed to Xabier Arrieta.

3 recordsLinked to original sources

arXiv2026

Extreme Optical Field Confinement and Enhancement in a Plasmonic Picopatch within a Nanoparticle-on-Mirror Resonator

Plasmonic resonances in metallic nanogaps can confine light into nanometric regions, but reaching modes of volume $\approx 1$ nm$^3$ remains challenging. We present a detailed theoretical analysis of the optical modes of an experimentally-motivated nanoresonator configuration that contains a picopatch formed by the lifting of a few gold atoms in the gap of a Nanoparticle-on-Mirror (NPoM) structure. Classical simulations indicate that the plasmonic modes associated with the picopatch geometry can confine light to extremely small regions and are highly sensitive to the picopatch size and shape, enabling broad tunability. Furthermore, these modes can couple strongly with other nanocavity modes of the structure, as identified from a clear anti-crossing behavior of the polaritonic resonances. Remarkably, up to $\approx 2000$-fold electric field enhancement inside the picopatch and tiny effective mode volumes approaching $\approx 1$ nm$^3$ are obtained. Further, changing the morphology of the picopatch does not modify the qualitative findings, and increasing the absorption losses in the classical simulations, to mimic quantum (non-local) effects in the metal permittivity, decreases the electric field enhancement only moderately. Compared to the standard picocavities formed by single-atom protrusions, picopatches are an intriguing alternative to reach extreme optical field confinement and enhancement in plasmonic cavities.

physics.optics↗

arXiv2026

Atomic-scale Stark-shift spectroscopy and microscopy of organic molecules

In conventional optical Stark-shift spectroscopy, molecules are exposed to spatially homogeneous static electric fields that shift the energies of their spectral lines. These shifts are attributed to the molecular electronic properties, such as variation of dipolar moment and polarizability of the molecule associated with photo(de)excitation. In realistic environments containing structural defects and nanoscale heterogeneities, however, molecules experience internal electric fields that vary strongly on the molecular scale, rendering the standard Stark selection rules inapplicable. Here we develop an extended theory of atomic-scale Stark shift, addressing such scenarios. Specifically, we present a detailed theoretical analysis of an experimentally relevant configuration where the atomically sharp tip of a light-assisted scanning tunneling microscope is used to controllably apply inhomogeneous electrostatic fields to representative molecular dyes spanning several molecular families. We decompose the total Stark shift into linear and quadratic contributions and show that they contain different information about the molecular properties. Concretely, spatial variations of the linear Stark shift as the tip scans across the molecule enable subnanometric mapping of the charge redistribution between ground and excited electronic states, with high sensitivity to molecular composition and chemical functionalization. The quadratic Stark contribution, in contrast, reflects changes in the conventional dipolar polarizability upon excitation. Together, these results establish nanoscale Stark-shift spectroscopy as a powerful tool for resolving excited-state charge dynamics in single molecules under realistic, strongly inhomogeneous electric fields.

physics.optics↗

arXiv2023

Fluorescent single-molecule STM probe

The plasmonic tip of a scanning tunnelling microscope (STM) is functionalized with a single fluorescent molecule and is scanned on a plasmonic substrate. The tunneling current flowing through the tip-molecule-substrate junction generates a narrow-line emission of light corresponding to the fluorescence of the negatively charged molecule suspended at the apex of the tip, i.e., the emission of the excited molecular anion (trion). The fluorescence of this molecular probe is recorded for tip-substrate nanocavities featuring different plasmonic resonances, for different tip-substrate distances and applied bias voltages, and on different substrates. We demonstrate that the width of the emission peak can be used as a probe of the trion-plasmon coupling strength and that the energy of the emitted photons is governed by the molecule interactions with its electrostatic environment. Additionally, we theoretically elucidate why the direct contact of the suspended molecule with the metallic tip does not totally quench the radiative emission of the molecule.

cond-mat.mes-hall↗