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George C. Schatz

Publications and source records attributed to George C. Schatz.

At least 19 recordsLinked to original sources

Quantum theory of surface lattice resonances

The collective interactions of nanoparticles arranged in periodic structures give rise to high-$Q$ in-plane diffractive modes known as surface lattice resonances. While these resonances and their broader implications have been extensively studied within the framework of classical electrodynamics and linear response theory, a quantum optical theory capable of describing the dynamics of these structures, especially in the presence of material nonlinearities beyond \textit{ad hoc} few-mode approximations, is largely missing. To this end, we consider a lattice of metallic nanoparticles coupled to the electromagnetic field and derive the quantum input--output relations within the electric dipole approximation. As applications, we analyze coupling between the nanoparticle array and external quantum emitters, and show how the formalism extends to molecular optomechanics, where the high $Q$-factors of SLRs enable coupling to collective vibrational modes. We further consider arrays composed of saturable excitonic emitters, demonstrating how emitter nonlinearities can be used to switch the SLR condition between electronic transitions. Using a perturbative approach that accounts for population dynamics, we show how these effects can be probed in pump--probe experiments and give rise to nonlinear phase-matching phenomena. Our work provides a microscopic framework for modeling SLRs interacting with quantum emitters without phenomenological descriptions of the electromagnetic environment.

quant-ph↗

The Role of Defect Geometry in Localized Emission from Monolayer Tungsten Dichalcogenides

Understanding the mechanism of single photon emission (SPE) in two-dimensional (2D) material is an unsolved problem important for quantum optical materials and the development of quantum information applications. In 2D transition metal dichalcogenides (TMDs) such as tungsten diselenide (WSe2), quantum emission has been broadly attributed to exciton localization from atomic point defects, yet the precise microscopic origins are not fully understood. This work introduces an empirically grounded computational framework that explains both the origins of facile SPE in WSe2 and its relative scarcity in related TMD, tungsten disulfide. High resolution microscopy identifies native defect geometries existing in monolayer WSe2 lattices providing the ingredients necessary to build a realistic model. The qualitative effects of chalcogen type, defect geometry, and mechanical strain on the electronic structure are then individually assessed using density functional theory, from which a specific divacancy configuration emerges as the candidate for localized single-electron transitions that match observed spectral energies. Spectroscopy and photon correlation measurements further validate this model, establishing a self-consistent link between defect geometry, electronic structure, and quantum emission. By isolating the distinct roles of chalcogen type, defect configuration, and mechanical strain, this work provides a thorough investigation of exciton localization and optical behavior, contributing to a clearer picture of the physical drivers of single photon emission in tungsten-based TMDs.

cond-mat.mtrl-sci↗

Real-Time Electron-Electron Scattering Dynamics in Plasmonic Nanostructures

Electron-electron scattering is one of the most important hot carrier relaxation pathways in plasmonic nanoparticles. Understanding the dynamics of this scattering process and the effects of this on excited state dephasing and relaxation is therefore essential for the design of plasmonic nanostructures, including optical properties and the dynamics of electrons in plasmon-driven catalytic reactions. In this work, we have developed a novel approach that incorporates real-time time-dependent density functional tight-binding (DFTB) simulations with the Lindblad quantum Boltzmann equation (LQBE) based on a screened electron-electron interaction that is determined by the random phase approximation (RPA). This approach enables a self-consistent description of electron-electron scattering effects that occur during and after plasmon excitation in clusters/nanoparticles with hundreds of atoms. With our RT-TDDFTB+LQBE method, we investigate the quasiparticle lifetime as well as population and coherence dynamics in silver, gold and aluminum nanoclusters with sizes between 1.5-2.6 nm. Our results show that the quasiparticle lifetimes and relaxation dynamics are highly energy dependent, becoming much faster at higher energies. For clusters less than 2 nm, quantum effects associated with discrete energy levels can lead to the fluctuating lifetimes and deviation of the dynamics from the typical thermalization process, while for larger nanoparticles, the transition to bulk metallic behavior is found. Decoherence of the initially excited plasmon resonance is observed with a timescale of 10 fs, much faster than population relaxation. For gold, we find that the 5d-band can significantly slow down the relaxation of energetic electrons though Auger scattering, and interband transitions can lead to a secondary decoherence process longer than 50 fs.

physics.chem-ph↗

A Surface-Scaffolded Molecular Qubit

Fluorescent spin qubits are central building blocks of quantum technologies. Placing these qubits at surfaces maximizes coupling to nearby spins and fields, enabling nanoscale sensing and facilitating integration with photonic and superconducting devices. However, reducing the dimensions or size of established qubit systems without sacrificing the qubit performance or degrading the coherence lifetime remains challenging. Here, we introduce a surface molecular qubit formed by pentacene molecules scaffolded on a two-dimensional (2D) material, hexagonal boron nitride (hBN). The qubit exhibits stable fluorescence and optically detected magnetic resonance (ODMR) from cryogenic to ambient conditions. With fully deuterated pentacene, the Hahn-echo coherence reaches 22 $μ$s and further extends to 214 $μ$s under dynamical decoupling, outperforming state-of-the-art shallow NV centers in diamond, despite being positioned directly on the surface. We map the local spin environment, resolving couplings to nearby nuclear and electron spins that can serve as auxiliary quantum resources. This platform combines true surface integration, long qubit coherence, and scalable fabrication, opening routes to quantum sensing, quantum simulation, and hybrid quantum devices. It also paves the way for a broader family of 2D material-supported molecular qubits.

quant-ph↗

Modifying the Optical Emission of Vanadyl Phthalocyanine via Molecular Self-Assembly on van der Waals Materials

Vanadyl phthalocyanine (VOPc) is a promising organic molecule for applications in quantum information because of its thermal stability, efficient processing, and potential as a spin qubit. The deposition of VOPc in different molecular orientations allows the properties to be customized for integration into various devices. However, such customization has yet to be fully leveraged to alter its intrinsic properties, particularly optical emission. Normally, VOPc films on dielectric substrates emit a broad photoluminescence peak in the near-infrared range, attributed to transitions in the Pc ring from its pi orbital structure. In this work, we demonstrate that the dominant optical transition of VOPc can be shifted by over 250 meV through the controlled deposition of thin films on van der Waals material substrates. The weak interactions with van der Waals materials allow the molecules to uniquely self-assemble, resulting in modified optical behavior modulated by molecular phase and thickness. This work connects the self-assembling properties of molecules with their altered electronic structures and the resulting optical emission.

cond-mat.mtrl-sci↗

High Temperature Quantum Emission from Covalently Functionalized van der Waals Heterostructures

Two-dimensional (2D) transition metal dichalcogenides (TMDs) are attractive nanomaterials for quantum information applications due to single photon emission (SPE) from atomic defects, primarily tungsten diselenide (WSe2) monolayers. Defect and strain engineering techniques have been developed to yield high purity, deterministically positioned SPE in WSe2. However, a major challenge in application of these techniques is the low temperature required to observe defect-bound TMD exciton emission, typically limiting SPE to T<30 K. SPE at higher temperatures either loses purity or requires integration into complex devices such as optical cavities. Here, 2D heterostructure engineering and molecular functionalization are combined to achieve high purity (>90%) SPE in strained WSe2 persisting to over T=90 K. Covalent diazonium functionalization of graphite in a layered WSe2/graphite heterostructure maintains high purity up to T=90 K and single-photon source integrity up to T=115 K. This method preserves the best qualities of SPE from WSe2 while increasing working temperature to more than three times the typical range. This work demonstrates the versatility of surface functionalization and heterostructure design to synergistically improve the properties of quantum emission and offers new insights into the phenomenon of SPE from 2D materials.

cond-mat.mtrl-sci↗

Density Functional Tight-Binding Enables Tractable Studies of Quantum Plasmonics

Routine investigations of plasmonic phenomena at the quantum level present a formidable computational challenge due to the large system sizes and ultrafast timescales involved. This Feature Article highlights the use of density functional tight-binding (DFTB), particularly its real-time time-dependent formulation (RT-TDDFTB), as a tractable approach to study plasmonic nanostructures from a purely quantum mechanical purview. We begin by outlining the theoretical framework and limitations of DFTB, emphasizing its efficiency in modeling systems with thousands of atoms over picosecond timescales. Applications of RT-TDDFTB are then explored in the context of optical absorption, nonlinear harmonic generation, and plasmon-mediated photocatalysis. We demonstrate how DFTB can reconcile classical and quantum descriptions of plasmonic behavior, capturing key phenomena such as size-dependent plasmon shifts and plasmon coupling in nanoparticle assemblies. Finally, we showcase DFTB's ability to model hot carrier generation and reaction dynamics in plasmon-driven \ch{H2} dissociation, underscoring its potential to model photocatalytic processes. Collectively, these studies establish DFTB as a powerful, yet computationally efficient tool to probe the emergent physics of materials at the limits of space and time.

cond-mat.mes-hall↗

Density Functional Tight-Binding Captures Plasmon-Driven H$_2$ Dissociation on Al Nanocrystals

Aluminum nanocrystals offer a promising platform for plasmonic photocatalysis, yet a detailed understanding of their electron dynamics and consequent photocatalytic performance has been challenging thus far due to computational limitations. Here, we employ density functional tight-binding methods (DFTB) to investigate the optical properties and H 2 dissociation dynamics of Al nanocrystals with varying sizes and geometries. Our real-time simulations reveal that Al's unique free-electron nature enables efficient light-matter interactions and rapid electronic thermalization. Cubic and octahedral nanocrystals ranging from 0.5 to 4.5 nm exhibit size-dependent plasmon resonances in the UV, with distinct spectral features arising from the particle geometry and electronic structure. By simulating H 2 dissociation near Al nanocrystals, we demonstrate that hot electrons generated through plasmon excitation can overcome the molecule's strong chemical bond within tens of femtoseconds. The laser intensity threshold is comparable to previous reports for Ag nanocrystals, though significantly lower than that of Au. Notably, the dipolar plasmon mode demonstrates higher efficiency for this reaction than the localized interband transition for particles at these sizes. Taken together, this work provides mechanistic insights into plasmon-driven catalysis and showcases DFTB's capability to study quantum plasmonics at unprecedented length and time scales.

cond-mat.mes-hall↗

Electron-Induced Radiation Chemistry in Environmental Transmission Electron Microscopy

Environmental transmission electron microscopy (E-TEM) enables direct observation of nanoscale chemical processes crucial for catalysis and materials design. However, the high-energy electron probe can dramatically alter reaction pathways through radiolysis - the dissociation of molecules under electron beam irradiation. While extensively studied in liquid-cell TEM, the impact of radiolysis in gas-phase reactions remains unexplored. Here, we present a numerical model elucidating radiation chemistry in both gas and liquid E-TEM environments. Our findings reveal that while gas-phase E-TEM generates radiolytic species with lower reactivity than liquid-phase systems, these species can accumulate to reaction-altering concentrations, particularly at elevated pressures. We validate our model through two case studies: the radiation-promoted oxidation of aluminum nanocubes and disproportionation of carbon monoxide. In both cases, increasing the electron beam dose rate directly accelerates their reaction kinetics, as demonstrated by enhanced AlOx growth and carbon deposition. Based on these insights, we establish practical guidelines for controlling radiolysis in closed-cell nanoreactors. This work not only resolves a fundamental challenge in electron microscopy but also advances our ability to rationally design materials with sub-Angstrom resolution.

cond-mat.mtrl-sci↗

Cooperative and Inhibitory Ion Transport in Functionalized Angstrom-Scale Two-Dimensional Channels

Significant success has been achieved in fabricating angstrom-scale artificial solid ionic channels aiming to replicate the biological ion channels (BICs).Besides high selectivity, BICs also exhibit sophisticated ion gating and interplay. However, such behavior and functionality are seldomly recreated in the artificial counterparts due to the insufficient understanding of the molecular origin. Here we report cooperative and inhibitory ion transport in angstrom-scale acetate functionalized MoS2 two dimensional channels.

physics.bio-ph↗

Plasmon Enhanced Spectroscopy and Photocatalysis

This study examines the Raman scattering and charge transfer properties of molecules adsorbed on the surface of a tetrahedral Au$_{120}$ nanoparticle based on the time-dependent density functional tight-binding (TD-DFTB) method. We study Raman scattering (SERS) enhancements for pyridine where the molecule is adsorbed either on the tip (V complex) or surface (S complex) of the nanoparticle. The scattering intensity is enhanced by a factor of 3-15 due to chemical effects while significantly larger enhancements (in the order of 10$^2$-10$^4$) are observed for plasmon resonance excitation at an energy of 2.5 eV depending on the adsorption site. Furthermore, we demonstrate charge transfer between the nanoparticle and a fullerene-based molecule after pulsed excitation of the plasmon resonance which shows how plasmon excitation can lead to negative molecular ion formation. All of these results are consistent with earlier studies using either TD-DFT theory or experimental measurements.

physics.chem-ph↗

Laser Pulse Induced Second- and Third-Harmonic Generation of Gold Nanorods with Real-Time Time-Dependent Density Functional Tight Binding (RT-TDDFTB) Method

In this study, we investigate second- and third-harmonic generation processes in Au nanorod systems using the real-time time-dependent density functional tight binding method. Our study focuses on the computation of nonlinear signals based on the time dependent dipole response induced by linearly polarized laser pulses interacting with nanoparticles. We systematically explore the influence of various laser parameters, including pump intensity, duration, frequency, and polarization directions, on harmonic generation. We demonstrate all the results using Au nanorod dimer systems arranged in end-to-end configurations, and disrupting the spatial symmetry of regular single nanorod systems is crucial for second-harmonic generation processes. Furthermore, we study the impact of nanorod lengths, which lead to variable plasmon energies, on harmonic generation, and estimates of polarizabilities and hyper-polarizabilities are provided.

physics.optics↗

Manipulating Two-Photon Absorption of Molecules through Efficient Optimization of Entangled Light

We report how the unique temporal and spectral features of pulsed entangled photons from a parametric downconversion source can be utilized for manipulating electronic excitations through the optimization of their spectral phase. A new comprehensive optimization protocol based on Bayesian optimization has been developed in this work to selectively excite electronic states accessible by two-photon absorption. Using our optimization method, the entangled two-photon absorption probability for a thiophene dendrimer can be enhanced by up to a factor of 20 while classical light turns out to be nonoptimizable. Moreover, the optimization involving photon entanglement enables selective excitation that would not be possible otherwise. In addition to optimization, we have explored entangled two-photon absorption in the small entanglement time limit showing that entangled light can excite molecular electronic states that are vanishingly small for classical light. We demonstrate these opportunities with an application to a thiophene dendrimer.

physics.chem-ph↗

Modeling of Collision-Induced Excitation and Quenching of Atomic Nitrogen

Excited atomic nitrogen atoms play an important role in plasma formation in hypersonic shock-waves, as happens during spacecraft reentry and other high velocity vehicle applications. In this study, we have thoroughly studied collision induced excitation (CIE) associated with two colliding nitrogen atoms in the N(4S), N(2D) and N(2P) states at collisions energies up to 6 eV, using time-independent scattering calculations to determine cross sections and temperature-dependent rate coefficients. The calculations are based on potential curves and couplings determined in earlier MRCI calculations with large basis sets, and the results are in good agreement with experiment where comparisons are possible. To properly consider the spin-orbit coupling matrix, we have developed a scaling method for treating transitions between different fine-structure components with calculations that only require calculations with two coupled states, and with this we define accurate degeneracy factors for determining cross sections and rate coefficients that include all states. The results indicate that both spin-orbit and derivative coupling effects can play important roles in collisional excitation and quenching, and that although derivative coupling is always much stronger than spin-orbit, there are many transitions where only spin-orbit can contribute. As part of this, we identify two distinct pathways associated with N(2D) relaxation, including one Auger-like mechanism leading to 2N(2D) that could be important at high temperature.

physics.chem-ph↗

Photodissociation of H$_2$ on Ag and Au Nanoparticles: Effect of Size, and Plasmon versus Inter-Band Transitions on Threshold Intensities for Dissociation

This paper provides new insights concerning the simulation of plasmon driven chemical reactions using real-time TDDFT based on the tight-binding electronic structure code DFTB+, with applications to the dissociation of H$_2$ on octahedral silver and gold nanoparticles with 19-489 atoms. A new component of these calculations involves sampling a 300 K canonical ensemble to determine the distribution of possible outcomes of the calculations, and with this approach we are able to determine the threshold for dissociation as a function of laser intensity, wavelength, and nanocluster size. We show that the threshold intensity varies as an inverse power of nanocluster size, which makes it possible to extrapolate the results to sizes that are more typical of experimental studies. The intensities obtained from this extrapolation are around a factor of 100 above powers used in the pulsed experiments. This is a closer comparison of theory and experiment than has been obtained in previous real-time simulations, and the remaining discrepancy can be understood in terms of electromagnetic hot spots that are associated with cluster formation. We also compare the influence of plasmon excitation versus inter-band excitation on reaction thresholds, revealing that for silver clusters plasmon excitation leads to lower thresholds, but for gold clusters, inter-band excitation is more effective. Our study also includes an analysis of charge transfer to and from the H$_2$ molecule, and a determination of orbital populations during and after the pulse, showing the correlation between metal excitations and the location of the antibonding level of H$_2$.

physics.chem-ph↗

Site-specific surface atom valence band structure via X-ray standing wave excited photoemission

X-ray standing wave (XSW) excited photoelectron emission was used to measure the site-specific valence band (VB) for 1/2 monolayer (ML) Pt grown on a SrTiO3 (001) surface. The XSW induced modulations in the core level (CL) and VB photoemission from the surface and substrate atoms were monitored for three hkl substrate Bragg reflections. The XSW CL analysis shows the Pt to have an fcc-like cube-on-cube epitaxy with the substrate. The XSW VB information compares well to a density functional theory calculated projected density of states from the surface and substrate atoms. Overall, this work represents a novel method for determining the contribution to the density of states by valence electrons from specific atomic surface sites.

cond-mat.mtrl-sci↗

Single-electron transport in a molecular Hubbard dimer

Many-body electron interactions are at the heart of chemistry and solid-state physics. Understanding these interactions is crucial for the development of molecular-scale quantum and nanoelectronic devices. Here, we investigate single-electron tunneling through an edge-fused porphyrin oligomer and demonstrate that its transport behavior is well described by the Hubbard dimer model. This allows us to study the role of electron-electron interactions in the transport setting. In particular, we empirically determine the molecule's on-site and inter-site electron-electron repulsion energies, which are in good agreement with density functional calculations, and establish the molecular electronic structure within various charge states. The gate-dependent rectification behavior is used to further confirm the selection rules and state degeneracies resulting from the Hubbard model. We therefore demonstrate that current flow through the molecule is governed by a non-trivial set of vibrationally coupled electronic transitions between various many-body states, and experimentally confirm the importance of electron-electron interactions in single-molecule devices.

cond-mat.mes-hall↗

Quantum electrodynamics description of localized surface plasmons at a metal nanosphere

A canonical quantization scheme for localized surface plasmons (LSPs) in a metal nanosphere is presented based on a microscopic model composed of electromagnetic fields, oscillators that describe plasmons, and a reservoir that describes excitations other than plasmons. The eigenmodes of this fully quantum electrodynamic theory show a spectrum that includes radiative depolarization and broadening, including redshifting from the quasi-static LSP modes, with increasing particle size. These spectral profiles correctly match those obtained with exact classical electrodynamics (Mie theory). The present scheme provides the electric fields per plasmon in both near- and far-field regions whereby its utility in the fields of quantum plasmonics and nano-optics is demonstrated.

cond-mat.mes-hall↗