arXiv subjects

Javier Aizpurua

Publications and source records attributed to Javier Aizpurua.

At least 19 recordsLinked to original sources

arXiv2026

Probing individual phonon-polaritonic nanoparticle-on-mirror cavities by infrared nanospectroscopy

Nanoparticle-on-mirror (NPoM) cavities enable extreme light confinement and strong light-matter interactions, but their realization with phonon-polariton materials in the mid-infrared spectral range remains largely unexplored. Here, we use nano-FTIR spectroscopy to study the near-field response of individual phononic NPoM cavities formed by gold nanoparticles on a quartz substrate supporting phonon-polaritons. By placing a metal tip on top of the NPoM and recording the tip-scattered field, we observe two reproducible cavity resonances, identified as the fundamental and a second-order antenna modes by numerical simulations. The calculations show that, in absence of the tip, the NPoM cavity exhibits ultrasmall mode volumes ($V \sim 10^3$ nm$^3$) and high quality factors ($Q \sim 100$), resulting in extraordinary field intensity enhancements ($F \sim 10^4$) and Purcell factors ($P_F \sim 10^9$). They also indicate that the nano-FTIR tip enables efficient excitation and readout of these phononic NPoM modes without perturbing them, while enhancing the intrinsic local field intensity in the NPoM gap by two orders of magnitude. Our results establish phononic NPoM cavities as a promising platform for mid-infrared nanophotonics and pave the way for ultrasensitive vibrational spectroscopy based on nano-FTIR measurements of individual cavities.

physics.optics↗

arXiv2026

Excitation of confined bulk plasmons in metallic nanoparticles by penetrating electron beams within a nonlocal analytical approach

Using a linear hydrodynamic model, we theoretically investigate the interaction between penetrating electron beams and sub-5-nm metallic spherical nanoparticles. We derive an analytical expression of the electron energy loss probability that includes nonlocal effects in the response of the confined electron gas. Our study focuses on the confined bulk plasmons (CBPs) which are inaccessible within local dielectric frameworks, and it shows that their excitation is highly sensitive to the impact parameter, the kinetic energy of the incident electron, and the nanoparticle size. In contrast to local approaches, our model predicts the emergence of several peaks associated with CBPs above the plasma frequency and a blueshift of their spectral envelope as the nanoparticle size decreases and the impact parameter of the electron beam increases. Moreover, it predicts a threshold impact parameter, corresponding to the minimum length of the electron's trajectory inside the nanoparticle required for efficient excitation of specific CBP modes. By exploiting a multipolar description of the CBPs, we identify the underlying selection rules governing their excitation by electron beams and correlate the observed blueshift at larger impact parameters with the preferential excitation of higher-order CBPs. The size-dependent dispersion of the CBPs further enhances this impact-parameter-dependent blueshift and also explains the decrease in the impact parameter threshold for smaller nanoparticles. The hydrodynamic model captures these trends without ad hoc momentum cutoffs and with rapid multipolar convergence. Applied to sodium nanoparticles as a canonical free-electron system, the theory reproduces qualitative behaviors observed in experiments and ab initio calculations, providing practical guidance for the design and interpretation of CBP-sensitive electron energy loss spectroscopy measurements.

cond-mat.mes-hall↗

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

Utility-scale quantum experiments using dynamic circuits to address collective dissipation in interacting qubits

Open quantum systems are central to quantum optics, condensed matter, and chemistry, yet their simulation remains challenging for both classical and near-term quantum hardware. In this work we implement and execute utility-scale quantum circuits that accurately reproduce the dissipative dynamics of interacting qubits. We consider a one-dimensional chain of many qubits weakly coupled to a common Markovian bath. The Markovian time evolution of the system is implemented through Trotterized evolution with the introduction of ancilla-assisted dissipative channels, including single-qubit and two-qubit dissipators to capture collective decay. Mid-circuit measurements, conditional gates, and hardware-aware transpilation significantly reduce circuit depth. We further implement a biased Clifford data regression (biased CDR), an error mitigation strategy that outperforms the uniform Cliffordization baseline and a variety of zero-noise extrapolation protocols. We execute large-scale quantum experiments of the dynamics of chains comprising up to 86 emitters on the IBM System Two \texttt{ibm\_basquecountry}. In order to do so, we use 129 total qubits (including ancillas), with the largest circuits contain about 8000 two-qubit gates. To validate these experiments we develop a classical Monte Carlo-Time-Evolving Block-Decimation (MC-TEBD) tensor-network method that incorporates reset operations through stochastic pure-state trajectories, obtaining very good agreement. The approach presented here opens a practical route for utility-scale quantum simulation of dissipative dynamics, enabled by dynamic circuits, targeted error mitigation, and tensor-network validation, and enables to tackle complex dynamics of systems such as quantum emitters in dissipative optical cavities.

quant-ph↗

arXiv2026

Addressing intramolecular vibrational redistribution in a single molecule through pump and probe surface-enhanced vibrational spectroscopy

The development of accurate tools to characterize Intramolecular Vibrational Redistribution (IVR) is of major interest in chemistry. In this context, surface-enhanced vibrational spectroscopies stand up as well-established techniques to study molecular vibrational lines and populations with a sensitivity that can reach the single-molecule level. However, to date, this possibility has not been fully developed to address IVR. Here, we establish a quantum mechanical framework based on molecular optomechanics that accounts for IVR, and we adopt it to analyze strategies to optimize IVR characterization by surface-enhanced vibrational spectroscopy. In particular, we model two different pump-and-probe configurations where the vibrational pumping is provided either by infrared laser illumination or by Stokes scattering processes in surface-enhanced Raman spectroscopy (SERS). We show for the two pumping configurations the existence of clear signatures on the anti-Stokes SERS spectra of population transfer between coupled vibrational modes in a molecule. Our calculations adopt realistic molecular and SERS parameters, suggesting that these signatures of IVR could be accessible at the single-molecule level within realistic experimental platforms.

physics.optics↗

arXiv2026

Addressing the correlation of Stokes-shifted photons emitted from two quantum emitters

In resonance fluorescence excitation experiments, light emitted from solid-state quantum emitters is typically filtered to eliminate the laser photons, ensuring that only red-shifted Stokes photons are detected. However, theoretical analyses of the fluorescence intensity correlation often model emitters as two-level systems, focusing on light emitted exclusively from the purely electronic transition (the zero-phonon line), or they rely on statistical approaches based on conditional probabilities that neglect the quantum coherence between the emitters and the coherence between the electric fields they generate. Here, we propose a model to characterize the correlation of either zero-phonon line photons or Stokes-shifted photons. This model successfully reproduces the experimental correlation of Stokes-shifted photons emitted from two interacting molecules and predicts that this correlation is affected by quantum coherence. Besides, we analyze the role of quantum coherence in the Stokes-shifted emission from two distant emitters, showing a sharp peak at zero time delay due to the Hanbury Brown--Twiss effect.

quant-ph↗

arXiv2026

Generation of polarization-entangled photon pairs from two interacting quantum emitters

Entangled photon pairs are key elements in quantum communication and quantum cryptography. State-of-the-art sources of entangled photons are mainly based on parametric down-conversion from nonlinear crystals, which is probabilistic in nature, and on cascade emission from biexciton quantum dots, which finds difficulties in generating entangled photons in the visible regime. Here, we use the Wigner-Weisskopf theory to provide a demonstration that polarization-entangled photon pairs can be emitted from two interacting quantum emitters with two-level-system behavior and perpendicular transition dipole moments. These emitters can represent a large variety of systems (e.g., organic molecules, quantum dots, and diamond color centers) offering a large technological versatility, for example, in the spectral regime of the emission. We show that a highly entangled photon pair can be postselected from this system by including optical filters. Additionally, we verify that the photon entanglement is not significantly affected by small changes in the detection directions and in the orientation between the dipole moments.

quant-ph↗

arXiv2026

Ultrafast optically induced tunneling in narrow metallic gaps from the time dependent density functional perspective

In this work, using the time-dependent density functional theory, we address the electron tunneling triggered by short (single-cycle and several-cycle) optical pulses in narrow metallic gaps under conditions relevant for actual experiments. We identify photon-assisted tunneling with one-photon, two-photon, and higher-order photon absorption, and we discuss the effect of the tunneling barrier, applied bias, and strength of the optical field on transition from photon-assisted tunneling (weak optical fields) to the optical field emission at strong optical fields. The numerical single-electron calculations and an analytical strong-field theory model are used to gain deeper insights into the results of the time-dependent density functional theory calculations. Additionally, our parameter-free calculations allow us to retrieve and explain recent experimental results on optically induced transport in narrow metallic gaps under an applied dc bias.

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↗

arXiv2026

Characterizing the Backscattered Spectrum of Mie Spheres

This study describes both experimentally and theoretically an important hitherto undiscovered feature of the scattering of micron_sized spherical objects when illuminated with highly focused circularly polarized light. This is a regime of high experimental relevance which has not been described in full detail. The experiments are complemented with the analytical formulas explaining the field scattered directed toward the backward hemispace. In particular, it is proven that this field shows a very regular oscillatory dependency with the optical size. This phenomenon is typically hidden in the total scattered field, as the field is scattered much less toward the backward hemisphere than toward the forward one. These regular oscillations are measured experimentally. It is proven that, by analyzing them, it is possible to determine the index of refraction of isolated micron_sized particles, opening new paths for applications in sensing and metrology.

physics.optics↗

arXiv2025

Roadmap on Nonlocality in Photonic Materials and Metamaterials

Photonic technologies continue to drive the quest for new optical materials with unprecedented responses. A major frontier in this field is the exploration of nonlocal (spatially dispersive) materials, going beyond the local, wavevector-independent assumption traditionally made in optical material modeling. On one end, the growing interest in plasmonic, polaritonic and quantum materials has revealed naturally occurring nonlocalities, emphasizing the need for more accurate models to predict and design their optical responses. This has major implications also for topological, nonreciprocal, and time-varying systems based on these material platforms. Beyond natural materials, artificially structured materials--metamaterials and metasurfaces--can provide even stronger and engineered nonlocal effects, emerging from long-range interactions or multipolar effects. This is a rapidly expanding area in the field of photonic metamaterials, with open frontiers yet to be explored. In the case of metasurfaces, in particular, nonlocality engineering has become a powerful tool for designing strongly wavevector-dependent responses, enabling enhanced wavefront control, spatial compression, multifunctional devices, and wave-based computing. Furthermore, nonlocality and related concepts play a critical role in defining the ultimate limits of what is possible in optics, photonics, and wave physics. This Roadmap aims to survey the most exciting developments in nonlocal photonic materials, highlight new opportunities and open challenges, and chart new pathways that will drive this emerging field forward--toward new scientific discoveries and technological advancements.

cond-mat.mes-hall↗

arXiv2025

Description of ultrastrong light-matter interaction through coupled harmonic oscillator models and their connection with cavity-QED Hamiltonians

Classical coupled harmonic oscillator models are capable of describing the optical and infrared response of nanophotonic systems where a cavity photon couples to dipolar matter excitations. The distinct forms of coupling adopted in these classical models leads to different results in the ultrastrong coupling regime. To clarify the specific classical model required to address particular configurations, we establish a connection between each oscillator model and the equivalent cavity Quantum Electrodynamics description. We show that the proper choice of coupled harmonic oscillator model depends on the presence or absence of the diamagnetic term in the quantum models, linked to whether transverse or longitudinal electromagnetic fields mediate the coupling. This analysis also shows how to exploit the classical oscillator models to extract measurable information of the optical response, as demonstrated in three canonical photonic systems, and to describe the opening of the Reststrahlen band in the bulk dispersion of phononic materials

quant-ph↗

arXiv2025

In-operando control of sum-frequency generation in tip-enhanced nanocavities

Sum-frequency generation (SFG) is a second-order nonlinear process widely used for characterizing surfaces and interfaces with monolayer sensitivity. Recently, optical field enhancement in plasmonic nanocavities has enabled SFG with continuous wave (CW) lasers from nanoscale areas of molecules, promising applications like nanoscale SFG spectroscopy and coherent upconversion for mid-infrared detection at visible frequencies. Here, we demonstrate CW SFG from individual nanoparticle-on-mirror (NPoM) cavities, which are resonant at visible frequencies and filled with a monolayer of molecules, when placed beneath a metal scanning probe tip. The tip acts as an efficient broadband antenna, focusing incident CW infrared illumination onto the nanocavity. The cascaded near-field enhancement within the NPoM nanocavity yields nonlinear optical responses across a broad range of infrared frequencies, achieving SFG enhancements of up to 14 orders of magnitude. Further, nanomechanical positioning of the tip allows for in-operando control of SFG by tuning the local field enhancement rather than the illumination intensities. The versatility of tip-enhanced nanocavities allows for SFG studies of a wide range of molecular species in the few-molecule regime without the need for complex nanofabrication of doubly-resonant nanocavities. Our results also promise SFG nanoimaging with tips providing strong visible and IR field enhancement at their apex, offering a robust platform for future applications in nonlinear nanooptics.

physics.optics↗

arXiv2024

Giant Purcell broadening and Lamb shift for DNA-assembled near-infrared quantum emitters

Controlling the light emitted by individual molecules is instrumental to a number of novel nanotechnologies ranging from super-resolution bio-imaging and molecular sensing to quantum nanophotonics. Molecular emission can be tailored by modifying the local photonic environment, for example by precisely placing a single molecule inside a plasmonic nanocavity with the help of DNA origami. Here, using this scalable approach, we show that commercial fluorophores experience giant Purcell factors and Lamb shifts, reaching values on par with those recently reported in scanning tip experiments. Engineering of plasmonic modes enables cavity-mediated fluorescence far detuned from the zero-phonon-line (ZPL) - at detunings that are up to two orders of magnitude larger than the fluorescence linewidth of the bare emitter and reach into the near-infrared. Our results evidence a regime where the emission linewidth is dominated by the excited state lifetime, as required for indistinguishable photon emission, baring relevance to the development of nanoscale, ultrafast quantum light sources and to the quest toward single-molecule cavity-QED. In the future, this approach may also allow to design efficient quantum emitters at infrared wavelengths, where standard organic sources have a reduced performance.

physics.optics↗

arXiv2024

Uncovering low-frequency vibrations in surface-enhanced Raman of organic molecules

Accessing the terahertz (THz) spectral domain through surface-enhanced Raman spectroscopy (SERS) is challenging and opens up the study of low-frequency molecular and electronic excitations. Compared to direct THz probing of heterogenous ensembles, the extreme plasmonic confinement of visible light to deep sub-wavelength scales allows the study of hundreds or even single molecules. We show that self-assembled molecular monolayers of a set of simple aromatic thiols confined inside single-particle plasmonic nanocavities can be distinguished by their low-wavenumber spectral peaks below 200 cm-1, after removal of a bosonic inelastic contribution and an exponential background from the spectrum Developing environment-dependent density-functional-theory simulations of the metal-molecule configuration enables the assignment and classification of their THz vibrations as well as the identification of intermolecular coupling effects and of the influence of the gold surface configuration Furthermore, we show dramatically narrower THz SERS spectra from individual molecules at picocavities, which indicates the possibility to study intrinsic vibrational properties beyond inhomogeneous broadening further supporting the key role of local environment.

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↗

arXiv2023

Giant optomechanical spring effect in plasmonic nano- and picocavities probed by surface-enhanced Raman scattering

Molecular vibrations couple to visible light only weakly, have small mutual interactions, and hence are often ignored for non-linear optics. Here we show the extreme confinement provided by plasmonic nano- and pico-cavities can sufficiently enhance optomechanical coupling so that intense laser illumination drastically softens the molecular bonds. This optomechanical pumping regime produces strong distortions of the Raman vibrational spectrum related to giant vibrational frequency shifts from an optical spring effect which is hundred-fold larger than in traditional cavities. The theoretical simulations accounting for the multimodal nanocavity response and near-field-induced collective phonon interactions are consistent with the experimentally-observed non-linear behavior exhibited in the Raman spectra of nanoparticle-on-mirror constructs illuminated by ultrafast laser pulses. Further, we show indications that plasmonic picocavities allow us to access the optical spring effect in single molecules with continuous illumination. Driving the collective phonon in the nanocavity paves the way to control reversible bond softening, as well as irreversible chemistry.

physics.optics↗

arXiv2023

Influence of direct dipole-dipole interactions on the optical response of 2D materials in strongly inhomogeneous infrared cavity fields

A two-dimensional (2D) material, formed for example by a self-assembled molecular monolayer or by a single layer of a van der Walls material, can couple efficiently with photonic nanocavities, potentially reaching the strong coupling regime. The coupling can be modelled using classical harmonic oscillator models or cavity quantum electrodynamics Hamiltonians that often neglect the direct dipole-dipole interactions within the monolayer. Here, we diagonalize the full Hamiltonian of the system, including these direct dipole-dipole interactions. The main effect on the optical properties of a typical 2D system is simply to renormalize the effective energy of the bright collective excitation of the monolayer that couples with the nanophotonic mode. On the other hand, we show that for situations of extreme field confinement, large transition dipole moments and low losses, fully including the direct dipole-dipole interactions is critical to correctly capture the optical response, with many collective states participating in it. To quantify this result, we propose a simple equation that indicates the condition for which the direct interactions strongly modify the optical response.

quant-ph↗