Chemistry Meets Plasmon Polaritons and Cavity Photons: A Perspective from Macroscopic Quantum Electrodynamics
Liang-Yan Hsu*
The interaction between light and molecules under quantum electrodynamics (QED) has long been less emphasized in physical chemistry, as semiclassical theories have dominated due to their relative simplicity. Recent experimental advances in polariton chemistry highlight the need for a theoretical framework that transcends traditional cavity QED and molecular QED models. Macroscopic QED is presented as a unified framework that seamlessly incorporates infinite photonic modes and dielectric environments, enabling applications to systems involving plasmon polaritons and cavity photons. This Perspective demonstrates the applicability of macroscopic QED to chemical phenomena through breakthroughs in molecular fluorescence, resonance energy transfer, and electron transfer. The macroscopic QED framework not only resolves the limitations of classical theories in physical chemistry but also achieves parameter-free predictions of experimental results, bridging quantum optics and material science. By addressing theoretical bottlenecks and unveiling new mechanisms, macroscopic QED establishes itself as an indispensable tool for studying QED effects on chemical systems.
Accelerating multipartite entanglement generation in non-Hermitian superconducting qubits
Chimdessa Gashu Feyisa, J-S You, Huan-Yu Ku and H H Jen
Open quantum systems are susceptible to losses in information, energy, and particles due to their surrounding environment. One novel strategy to mitigate these losses is to transform them into advantages for quantum technologies through tailored non-Hermitian quantum systems. In this work, we theoretically propose a fast generation of multipartite entanglement in non-Hermitian qubits. Our findings reveal that weakly coupled non-Hermitian qubits can accelerate multiparty entanglement generation by thousands of times compared to Hermitian qubits, in particular when approaching the 2^n-th order exceptional points of n qubits in the PT-symmetric regime. Furthermore, we show that Hermitian qubits can generate GHZ states with a high fidelity more than 0.9995 in a timescale comparable to that of non-Hermitian qubits, but at the expense of intense driving and large coupling constant. Our approach is scalable to a large number of qubits, presenting a promising pathway for advancing quantum technologies through the non-Hermiticity and higher-order exceptional points in many-body quantum systems.
Non-Adiabatic Quantum Electrodynamic Effects on Electron–Nucleus–Photon Systems: Single Photonic Mode vs Infinite Photonic Modes [Feature Article]
Chih-En Shen, Hung-Sheng Tsai, Liang-Yan Hsu*
The quantum-electrodynamic non-adiabatic emission (QED-NAE) is a type of radiatively assisted vibronic de-excitation due to electromagnetic vacuum fluctuations on non-adiabatic processes. Building on our previous work [Tsai et al., J. Phys. Chem. Lett. 14, 5924 (2023)], we extend the theory of the QED-NAE rate from a single cavity photonic mode to infinite photonic modes and calculate the QED-NAE rates of 9-cyanoanthracene at the first-principles level. To avoid the confusion, the quantum electrodynamic internal conversion process is renamed as “QED-NAE” in our present work. According to our theory, we identify three key factors influencing the QED-NAE processes: light–matter coupling strength (mode volume), mass-weighted orientation factor, and photonic density of states. The mode volume is the primary factor causing rate differences between the two scenarios. In a single cavity with a small mode volume, strong light–matter coupling strength boosts QED-NAE rates. In contrast, in free space with infinite photonic modes, weak coupling strength significantly reduces these rates. From a single cavity photonic mode to infinite photonic modes, the mass-weighted orientation factor only causes an 8π/3-fold increase in the QED-NAE rate. In free space, the photonic density of state exhibits a flat and quadratic distribution, which slightly reduces the QED-NAE rate. Our study shows that cavities can significantly enhance non-adiabatic QED effects while providing a robust analysis demonstrating that QED vibronic effects can be safely ignored in free space.
Point Spread Function Engineering for Spiral Phase Interferometric Scattering Microscopy Enables Robust 3D Single-Particle Tracking and Characterization
Nathan J. Brooks, Chih-Chen Liu, Yan-Hsien Chen, and Chia-Lung Hsieh*
Interferometric scattering (iSCAT) microscopy is currently among the most powerful techniques available for achieving high-sensitivity single-particle localization. This capability is realized through homodyne detection, where interference with a reference wave offers the promise of exceptionally precise three-dimensional (3D) localization. However, the practical application of iSCAT to 3D tracking has been hampered by rapid oscillations in the signal-to-noise ratio (SNR) as particles move along the axial direction. In this study, we introduce a novel strategy based on back pupil plane engineering, wherein a spiral phase mask is used to redistribute the phase of the scattered field of the particle uniformly across phase space, thus ensuring consistent SNR as the particle moves throughout the focal volume. Our findings demonstrate that this modified spiral phase iSCAT exhibits greatly enhanced localizability characteristics. Additionally, the uniform phase distribution enables reliable characterization of the particle’s optical properties regardless of its position. We substantiate our theoretical results with numerical and experimental demonstrations, showcasing the practical application of this approach for high-precision, ultrahigh-speed (20,000 frames per second) 3D tracking and polarizability measurement of freely diffusing nanoparticles as small as 20 nm.
Tungsten Nitride (W5N6): An Ultraresilient 2D Semimetal
Two-dimensional transition metal nitrides offer intriguing possibilities for achieving novel electronic and mechanical functionality owing to their distinctive and tunable bonding characteristics compared to other 2D materials. We demonstrate here the enabling effects of strong bonding on the morphology and functionality of 2D tungsten nitrides. The employed bottom-up synthesis experienced a unique substrate stabilization effect beyond van-der-Waals epitaxy that favored W5N6 over lower metal nitrides. Comprehensive structural and electronic characterization reveals that monolayer W5N6 can be synthesized at large scale and shows semimetallic behavior with an intriguing indirect band structure. Moreover, the material exhibits exceptional resilience against mechanical damage and chemical reactions. Leveraging these electronic properties and robustness, we demonstrate the application of W5N6 as atomic-scale dry etch stops that allow the integration of high-performance 2D materials contacts. These findings highlight the potential of 2D transition metal nitrides for realizing advanced electronic devices and functional interfaces.
Enhancing the Electrochemical Activity of 2D Materials Edges through Oriented Electric Fields
The edges of 2D materials have emerged as promising electrochemical catalyst systems, yet their performance still lags behind that of noble metals. Here, we demonstrate the potential of oriented electric fields (OEFs) to enhance the electrochemical activity of 2D materials edges. By atomically engineering the edge of a fluorographene/graphene/MoS2 heterojunction nanoribbon, strong and localized OEFs were realized as confirmed by simulations and spatially resolved spectroscopy. The observed fringing OEF results in an enhancement of the heterogeneous charge transfer rate between the edge and the electrolyte by 2 orders of magnitude according to impedance spectroscopy. Ab initio calculations indicate a field-induced decrease in the reactant adsorption energy as the origin of this improvement. We apply the OEF-enhanced edge reactivity to hydrogen evolution reactions (HER) and observe a significantly enhanced electrochemical performance, as evidenced by a 30% decrease in Tafel slope and a 3-fold enhanced turnover frequency. Our findings demonstrate the potential of OEFs for tailoring the catalytic properties of 2D material edges toward future complex reactions.
Te-I Liu*, Jhih-Shan Wang, Ai-Phuong Nguyen, Marco Raabe, Carlos Jose Quiroz Reyes, Chih-Hsin Lin, Ching-Wei Lin*
Cytometry plays a crucial role in characterizing cell properties, but its restricted optical window (400-850 nm) limits the number of stained fluorophores that can be detected simultaneously and hampers the study and utilization of short-wave infrared (SWIR; 900-1,700 nm) fluorophores in cells. Here we introduce two SWIR-based methods to address these limitations: SWIR flow cytometry and SWIR image cytometry. We develop a quantification protocol for deducing cellular fluorophore mass. Both systems achieve a limit of detection of ~0.1 fg cell−1 within a 30-min experimental timeframe, using individualized, high-purity (6,5) single-wall carbon nanotubes as a model fluorophore and macrophage-like RAW264.7 as a model cell line. This high-sensitivity feature reveals that low-dose (6,5) serves as an antioxidant, and cell morphology and oxidative stress dose-dependently correlate with (6,5) uptake. Our SWIR cytometry holds immediate applicability for existing SWIR fluorophores and offers a solution to the issue of spectral overlapping in conventional cytometry.
Accurate kinetic studies of OH + HO2 radical–radical reaction through direct measurement of precursor and radical concentrations with high-resolution time-resolved dual-comb spectroscopy
I-Yun Chen, Che-Wei Chang, Christa Fittschen, and Pei-Ling Luo*
The radical–radical reaction between OH and HO2 has been considered for a long time as an important reaction in tropospheric photochemistry and combustion chemistry. However, a significant discrepancy of an order of magnitude for rate coefficients of this reaction is found between two recent experiments. Herein, we investigate the reaction OH + HO2 via direct spectral quantification of both the precursor (H2O2) and free radicals (OH and HO2) upon the 248 nm photolysis of H2O2 using infrared two-color time-resolved dual-comb spectroscopy. With quantitative and kinetic analysis of concentration profiles of both OH and HO2 at varied conditions, the rate coefficient kOH+HO2 is determined to be (1.10 ± 0.12) × 10–10 cm3 molecule–1 s–1 at 296 K. Moreover, we explore the kinetics of this reaction under conditions in the presence of water, but no enhancement in the kOH+HO2 can be observed. This work as an independent experiment plays a crucial role in revisiting this prototypical radical–radical reaction.
Generating scalable graph states in an atom-nanophotonic interface
C.-H. Chien, S. Goswami, C.-C. Wu, W.-S. Hiew, Y.-C. Chen, and H. H. Jen
Scalable graph states are essential for measurement-based quantum computation and many entanglement-assisted applications in quantum technologies. Generation of these multipartite entangled states requires a controllable and efficient quantum device with delicate design of generation protocol. Here we propose to prepare high-fidelity and scalable graph states in one and two dimensions, which can be tailored in an atom-nanophotonic cavity via state carving technique. We propose a systematic protocol to carve out unwanted state components, which facilitates scalable graph states generations via adiabatic transport of a definite number of atoms in optical tweezers. An analysis of state fidelity is also presented, and the state preparation probability can be optimized via multiqubit state carvings and sequential single-photon probes. Our results showcase the capability of an atom-nanophotonic interface for creating graph states and pave the way toward novel problem-specific applications using scalable high-dimensional graph states with stationary qubits.
1Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei City 106319, Taiwan 2Department of Medical Research, Hualien Tzu Chi Hospital, Buddhist Tzu Chi Medical Foundation, Hualien City 970, Taiwan 3National Synchrotron Radiation Research Center, Hsinchu City 300092, Taiwan 4Tzu-Chi University of Science and Technology, Hualien City 970, Taiwan 5Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei City 106335, Taiwan 6Department of Chemistry, National Taiwan Normal University, Taipei City 106, Taiwan
Extreme ultraviolet (EUV) radiation with wavelengths of 10 – 121 nm has drawn considerable attention recently for its use in photolithography to fabricate nanoelectronic chips. This study demonstrates, for the first time, fluorescent nanodiamonds (FNDs) with nitrogen-vacancy (NV) centers as scintillators to image and characterize EUV radiations. The FNDs employed are ~100 nm in size; they form a uniform and stable thin film on an indium tin oxide-coated slide by electrospray deposition. The film is non-hygroscopic, photostable, and can emit bright red fluorescence from NV0 centers when excited by EUV light. An FND-based imaging device has been developed and applied for beam diagnostics of 50 nm and 13.5 nm synchrotron radiations, achieving a spatial resolution of 30 μm using a film of ~1 μm thickness. The noise equivalent power density is 29 μW/cm2Hz1/2 for the 13.5 nm radiation. The method is generally applicable to imaging EUV radiations from different sources.
Direct gas-phase formation of formic acid through reaction of Criegee intermediates with formaldehyde
Pei-Ling Luo*, I-Yun Chen, M. Anwar H. Khan, and Dudley E. Shallcross
Ozonolysis of isoprene is considered to be an important source of formic acid (HCOOH), but its underlying reaction mechanisms related to HCOOH formation are poorly understood. Here, we report the kinetic and product studies of the reaction between the simplest Criegee intermediate (CH2OO) and formaldehyde (HCHO), both of which are the primary products formed in ozonolysis of isoprene. By utilizing time-resolved infrared laser spectrometry with the multifunctional dual-comb spectrometers, the rate coefficient kCH2OO+HCHO is determined to be (4.11 ± 0.25) × 10−12 cm3 molecule−1 s−1 at 296 K and a negative temperature dependence of the rate coefficient is observed and described by an Arrhenius expression with an activation energy of (–1.81 ± 0.04) kcal mol−1. Moreover, the branching ratios of the reaction products HCOOH + HCHO and CO + H2O + HCHO are explored. The yield of HCOOH is obtained to be 37–54% over the pressure (15–60 Torr) and temperature (283–313 K) ranges. The atmospheric implications of the reaction CH2OO + HCHO are also evaluated by incorporating these results into a global chemistry-transport model. In the upper troposphere, the percent loss of CH2OO by HCHO is found by up to 6% which can subsequently increase HCOOH mixing ratios by up to 2% during December-January-February months.
Our latest publication employed PalmGRET, a bioluminescence-resonance-energy-transfer (BRET)-based EV reporter, to discover an abundant release of big EVs (bEVs; >200 nm) by aggressive breast cancers when compared to epithelial and less malignant cells. bEVs have been largely overshadowed by small EVs (sEVs; <200 nm) in EV research in the past decades. This is the first study to accurately detect and systematically compare biophysical property and in vivo profiles of breast cancer bEVs and sEVs. This is followed by the identification of EV surface oncoproteins, and their role in modulating organotropism and tumorigenic potential of the bEVs and sEVs. Our landmark findings impart a broad and deep reference for upcoming EV studies, with an emphasis on EV engineering for diagnosis and therapeutic applications.