Time-resolved Absorption Spectroscopy Research Articles

Improving Three-Photon Fluorescence of Near-Infrared Quantum Dots for Deep Brain Imaging by Suppressing Biexciton Decay.

Three-photon fluorescence microscopy (3PFM) is a promising brain research tool with submicrometer spatial resolution and high imaging depth. However, only limited materials have been developed for 3PFM owing to the rigorous requirement of the three-photon fluorescence (3PF) process. Herein, under the guidance of a band gap engineering strategy, CdTe/CdSe/ZnS quantum dots (QDs) emitting in the near-infrared window are designed for constructing 3PF probes. The formation of type II structure significantly increased the three-photon absorption cross section of QDs and caused the delocalization of electron-hole wave functions. The time-resolved transient absorption spectroscopy confirmed that the decay of biexcitons was significantly suppressed due to the appropriate band gap alignment, which further enhanced the 3PF efficiency of QDs. By utilizing QD-based 3PF probes, high-resolution 3PFM imaging of cerebral vasculature was realized excited by a 1600 nm femtosecond laser, indicating the possibility of deep brain imaging with these 3PF probes.

Tracking nuclear motion in single-molecule magnets using femtosecond X-ray absorption spectroscopy

The development of new data storage solutions is crucial for emerging digital technologies. Recently, all-optical magnetic switching has been achieved in dielectrics, proving to be faster than traditional methods. Despite this, single-molecule magnets (SMMs), which are an important class of magnetic materials due to their nanometre size, remain underexplored for ultrafast photomagnetic switching. Herein, we report femtosecond time-resolved K-edge X-ray absorption spectroscopy (TR-XAS) on a Mn(III)-based trinuclear SMM. Exploiting the elemental specificity of XAS, we directly track nuclear dynamics around the metal ions and show that the ultrafast dynamics upon excitation of a crystal-field transition are dominated by a magnetically active Jahn-Teller mode. Our results, supported by simulations, reveal minute bond length changes from 0.01 to 0.05 Å demonstrating the sensitivity of the method. These geometrical changes are discussed in terms of magneto-structural relationships and consequently our results illustrate the importance of TR-XAS for the emerging area of ultrafast molecular magnetism.

Near-infrared two-photon absorption and excited state dynamics of a fluorescent diarylethene derivative.

Near-infrared two-photon absorption and excited state dynamics of a fluorescent diarylethene (fDAE) derivative were investigated by time-resolved absorption and fluorescence spectroscopies. Prescreening with quantum chemical calculation predicted that a derivative with methylthienyl groups (mt-fDAE) in the closed-ring isomer has a two-photon absorption cross-section larger than 1000 GM, which was experimentally verified by Z-scan measurements and excitation power dependence in transient absorption. Comparison of transient absorption spectra under one-photon and simultaneous two-photon excitation conditions revealed that the closed-ring isomer of mt-fDAE populated into higher excited states deactivates following three pathways on a timescale of ca. 200fs: (i) the cycloreversion reaction more efficient than that by the one-photon process, (ii) internal conversion into the S1 state, and (iii) relaxation into a lower state (S1' state) different from the S1 state. Time-resolved fluorescence measurements demonstrated that this S1' state is relaxed to the S1 state with the large emission probability. These findings obtained in the present work contribute to extension of the ON-OFF switching capability of fDAE to the biological window and application to super-resolution fluorescence imaging in a two-photon manner.

Poly(2-oxazoline) Amphiphilicity Tunes the Excited-State Proton Transfer of Pyrenol-based Polyphotoacids.

The ability of light to change the properties of light-responsive polymers opens avenues for targeted release of cargo with a high degree of spatial and temporal control. Recently, we established photoacid polymers as light-switchable macromolecular amphiphiles. In these systems, light-induced excited-state proton transfer (ESPT) causes changes in amphilicity. However, as the intermolecular process itself critically depends on the local environment of the photoacid unit within the polymer, the overall amphiphilicity directly influences ESPT. Thus, understanding the impact of the local environment on the photophysics of photoacidic side chains is key to material design. In this contribution we address both thermodynamic and kinetic aspects of ESPT in oxazoline-based amphiphilic polymers with pyrenol-based photoacid side chains. We will compare the effect of polymer design, i.e. statistical and block arrangements, i.e. in poly[(2-ethyl-2-oxazoline)-co-(1-(6/8-hydroxyperene)sulphonylaziridine)] and poly(2-ethyl-2-oxazoline)-block-poly[(2-ethyl-2-oxazoline)-co-(2-(3-(6-hydroxypyrene)sulphona mide)propyl-2-oxazoline), on the intermolecular proton transfer reaction by combining steady-state and time-resolved absorption and emission spectroscopy. ESPT appears more prominent in the statistical copolymer compared to a block copolymer with overall similar pyrenol loading. We hypothesize that the difference is due to different local chain arrangements adopted by the polymers in the two cases.

Excited-State Identification of a Nickel-Bipyridine Photocatalyst by Time-Resolved X-ray Absorption Spectroscopy.

Photoassisted catalysis using Ni complexes is an emerging field for cross-coupling reactions in organic synthesis. However, the mechanism by which light enables and enhances the reactivity of these complexes often remains elusive. Although optical techniques have been widely used to study the ground and excited states of photocatalysts, they lack the specificity to interrogate the electronic and structural changes at specific atoms. Herein, we report metal-specific studies using transient Ni L- and K-edge X-ray absorption spectroscopy of a prototypical Ni photocatalyst, (dtbbpy)Ni(o-tol)Cl (dtb = 4,4'-di-tert-butyl, bpy = bipyridine, o-tol = ortho-tolyl), in solution. We unambiguously confirm via direct experimental evidence that the long-lived (∼5 ns) excited state is a tetrahedral metal-centered triplet state. These results demonstrate the power of ultrafast X-ray spectroscopies to unambiguously elucidate the nature of excited states in important transition-metal-based photocatalytic systems.

Shock-Tube Measurements of Carbon Monoxide During Combustion of Hydroxyl-Terminated Polybutadiene Products/Air

Hydroxyl-terminated polybutadiene (HTPB) is a fuel proposed for use in hypersonic rockets, specifically in solid fuel ramjets (SFRJs), where it combines with air and undergoes combustion processes that range from fuel pyrolysis to fuel lean- combustion. A better understanding and the improvement of SFRJ combustion can be accomplished through fundamental experiments and computational fluid dynamics modeling. The current chemical-kinetic models need data to capture the reaction kinetics at the conditions under which SFRJs operate. This work focuses on providing combustion data to assess the predictive capabilities of state-of-the-art mechanisms at conditions relevant to SFRJs. The University of Central Florida shock-tube facility was used to conduct experiments of various combinations of HTPB products in air near 5 atm for temperatures ranging from 1100 to 1800 K and Φ=0.5, 1.0, 4.76. Nonintrusive, time-resolved laser absorption spectroscopy was used to record carbon-monoxide-concentration time histories and compared against the predictions of AramcoMech3.0 and HyChem mechanisms. For each mixture, the mid- and high-temperature conditions matched the models well, whereas there was a significant discrepancy for the low-temperature condition. A sensitivity analysis was then conducted to determine which reactions warranted further investigation to address the discrepancy at low temperatures.

Influence of the RF voltage amplitude on the space- and time-resolved properties of RF–LF dielectric barrier discharges in α–γ mode

This work reports the results of an experimental and modeling study on dual-frequency Ar–NH3 dielectric barrier discharges (DBDs) exhibiting the α–γ transition. A combination of space- and time-resolved optical absorption and emission spectroscopy is used to record spatio-temporal mappings of the Ar metastable number density, Ar 750.4 nm line emission intensity, and electron–Ar bremsstrahlung continuum emission intensity. With the increase of the radio frequency (RF) voltage amplitude in a 50 kHz–5 MHz DBD, maximum populations of Ar excited species (1s and 2p states, linked to the population of high-energy electrons) observed in the γ mode decrease and appear earlier in the low-frequency cycle. On the other hand, the density of the bulk electrons, monitored from the continuum emission intensity, increases, with a more prominent rise in the RF-α mode than in the γ regime. Such behaviors are consistent with the predictions of 1D fluid model and results from a decrease of the gas voltage required for self-maintenance of the cathode sheath in the γ breakdown.

Modulation of Photoinduced Phase Segregation and Stress-Driven Nanoscale Cracking in Hybrid Halide Perovskite Solar Cells.

The negative effect of photoinduced halide segregation (PIHS) on the properties of hybrid halide perovskites poses a major obstacle for its future commercial application. Therefore, the in-depth understanding of halide-ion segregation and its causes is an urgent and intractable problem. When PIHS reaches a certain threshold, it will aggravate the deterioration of the film surface morphology and form nanoscale cracks. Herein, the formation mechanism and types of cracks are revealed by exploring the stress distribution in the film. Using the femtosecond time-resolved transient absorption spectroscopy, the ultrafast formation of the iodine rich phase is observed, which appears earlier than the bromine rich phase. In addition, the introduction of organic ligand didodecyldimethylammonium bromide can significantly inhibit PIHS and improve the surface morphology of the film, which can promote the device efficiency from 9.63 to 11.20%. This work provides a novel perspective for the exploration of the PIHS.

Near-IR-Absorbing Bis-Donor Functionalized Aza-BODIPY Derivatives: Synthesis and Photophysical Study by Using Transient Optical Spectroscopy.

A series of near-IR absorbing 2,6-diarylated BF2-chelated aza-boron-dipyrromethenes (aza-BDPs) derivatives bearing different electron donors (benzene, naphthalene, phenanthrene, phenothiazine and carbazole) were designed and synthesized. The effect of different electron donor substitutions on the photophysical properties was studied by steady-state UV-vis absorption and fluorescence spectra, electrochemical, time-resolved nanosecond transient absorption (ns-TA) spectroscopy and theoretical computations. The UV-vis absorption spectra of AzaBDP-PTZ and AzaBDP-CAR (λabs=710 nm in toluene) showed a bathochromic absorption profile compared with the reference AzaBDP-Ph (λabs=685 nm in toluene), indicating the non-negligible electronic interaction at the ground state between donor and acceptor moieties. Moreover, the fluorescence is almost completely quenched for AzaBDP-PTZ/AzaBDP-CAR (fluorescence quantum yield, ΦF=0.2-0.7 % in toluene) as compared with the AzaBDP-Ph (ΦF=27 % in toluene). However, the apparent intersystem crossing ability of these compounds is poor, based on the singlet oxygen quantum yield (ΦΔ=0.3-1.5 %). The ns-TA spectral study showed typical Bodipy localized triplet state transient features, short-lived excited triplet state for AzaBDP-Ph (τT=53.2 μs) versus significantly long-lived triplet state for AzaBDP-CAR (τT=114 μs) was observed under deaerated experimental conditions. These triplet state lifetimes are much longer than that obtained with diiodoAzaBDP (intramolecular heavy atom effect, τT=1.5~7.2 μs). These information are useful for molecular structure design of triplet photosensitizers, for which longer triplet state lifetimes are usually desired. Theoretical computations displayed that the triplet state is mainly localized on the AzaBDP core, moreover, it was found that the HOMO/LUMO energy gap decreased after introducing donor moieties to the skeleton as compared with the reference.

Halide Engineering in Mixed Halide Perovskite-Inspired Cu2AgBiI6 for Solar Cells with Enhanced Performance.

Cu2AgBiI6 (CABI) is a promising perovskite-inspired absorber for solar cells due to its direct band gap and high absorption coefficient. However, the nonradiative recombination caused by the high extrinsic trap density limits the performance of CABI-based solar cells. In this work, we employ halide engineering by doping bromide anions (Br-) in CABI thin films, in turn significantly improving the power conversion efficiency (PCE). By introducing Br- in the synthetic route of CABI thin films, we identify the optimum composition as CABI-10Br (with 10% Br at the halide site). The tailored composition appears to reduce the deep trap density as shown by time-resolved photoluminescence and transient absorption spectroscopy characterizations. This leads to a dramatic increase in the lifetime of charge carriers, which therefore improves both the external quantum efficiency and the integrated short-circuit current. The photovoltaic performance shows a significant boost since the PCE under standard 1 sun illumination increases from 1.32 to 1.69% (∼30% relative enhancement). Systematic theoretical and experimental characterizations were employed to investigate the effect of Br- incorporation on the optoelectronic properties of CABI. Our results highlight the importance of mitigating trap states in lead-free perovskite-inspired materials and that Br- incorporation at the halide site is an effective strategy for improving the device performance.

Kinetics of the Gas-Phase Reactions of syn- and anti-CH3CHOO Criegee Intermediate Conformers with SO2 as a Function of Temperature and Pressure.

Kinetics of reactions between SO2 and CH3CHOO Criegee intermediate conformers have been measured at temperatures between 242 and 353 K and pressures between 10 and 600 Torr using laser flash photolysis of CH3CHI2/O2/N2/SO2 gas mixtures coupled with time-resolved broadband UV absorption spectroscopy. The kinetics of syn-CH3CHOO + SO2 are pressure-dependent and exhibit a negative temperature dependence, with the observed pressure dependence reconciling apparent discrepancies between previous measurements performed at ∼298 K. Results indicate a rate coefficient of (4.80 ± 0.46) × 10-11 cm3 s-1 for the reaction of syn-CH3CHOO with SO2 at 298 K and 760 Torr. In contrast to the behavior of the syn-conformer, the kinetics of anti-CH3CHOO + SO2 display no significant dependence on temperature or pressure over the ranges investigated, with a mean rate coefficient of (1.18 ± 0.21) × 10-10 cm3 s-1 over all conditions studied in this work. Results indicate that the reaction of syn-CH3CHOO with SO2 competes with unimolecular decomposition and reaction with water vapor in areas with high SO2 concentration and low humidity, particularly at lower temperatures.

Shell thickness influence on the carrier dynamics of InP/ZnS QDs

InP/ZnS core/shell quantum dots (QDs) have been widely applied in many fields due to their excellent luminescence performance. In this study, the correlation between the ZnS shell thickness and the ultrafast carrier dynamics in InP/ZnS QDs was investigated by using femtosecond time-resolved transient absorption spectroscopy and time-resolved photoluminescence techniques. We found that a thicker ZnS shell could confine more carriers to the InP core, thus effectively weakening the interactions between the carriers in the core and the interfacial defect states; this further enhanced the quantum yields and photoluminescence properties in InP/ZnS QDs.

Efficient prediction of attosecond two-colour pulses from an X-ray free-electron laser with machine learning

X-ray free-electron lasers are sources of coherent, high-intensity X-rays with numerous applications in ultra-fast measurements and dynamic structural imaging. Due to the stochastic nature of the self-amplified spontaneous emission process and the difficulty in controlling injection of electrons, output pulses exhibit significant noise and limited temporal coherence. Standard measurement techniques used for characterizing two-coloured X-ray pulses are challenging, as they are either invasive or diagnostically expensive. In this work, we employ machine learning methods such as neural networks and decision trees to predict the central photon energies of pairs of attosecond fundamental and second harmonic pulses using parameters that are easily recorded at the high-repetition rate of a single shot. Using real experimental data, we apply a detailed feature analysis on the input parameters while optimizing the training time of the machine learning methods. Our predictive models are able to make predictions of central photon energy for one of the pulses without measuring the other pulse, thereby leveraging the use of the spectrometer without having to extend its detection window. We anticipate applications in X-ray spectroscopy using XFELs, such as in time-resolved X-ray absorption and photoemission spectroscopy, where improved measurement of input spectra will lead to better experimental outcomes.

Probing the Dynamic Landscape: from Static to Time-Resolved X-ray Absorption Spectroscopy to Investigate Copper Redox Chemistry in Neurodegenerative Disorders.

Copper (Cu), capable of existing in various oxidation states, notably Cu(I) and Cu(II), plays a pivotal role in diverse biological redox reactions. This includes its involvement in pathways associated with oxidative stress in neurodegenerative disorders such as Alzheimer's disease, Parkinson's disease, and Transmissible Spongiform Encephalopathies. This paper offers an overview of X-ray Absorption Spectroscopy (XAS) studies designed to elucidate the interactions between Cu ions and proteins or peptides associated with these neurodegenerative diseases. The emphasis lies on the technique's specificity, revealing the local coordination environment, and on its sensitivity to Cu oxidation states. Furthermore, the paper focuses on XAS applications targeting the characterization of intermediate reaction states and explores the opportunities arising from recent advancements in time-resolved XAS at ultra-bright synchrotron and free electron laser radiation sources.

Charge Trapping in Semiconductor Photocatalysts: A Time- and Space-Domain Perspective.

Harnessing solar energy to produce value-added fuels and chemicals through photocatalysis techniques holds promise for establishing a sustainable and environmentally friendly energy economy. The intricate dynamics of photogenerated charge carriers lies at the core of the photocatalysis. The balance between charge trapping and band-edge recombination has a crucial influence on the activity of semiconductor photocatalysts. Consequently, the regulation of traps in photocatalysts becomes the key to optimizing their activities. Nevertheless, our comprehension of charge trapping, compared to that of well-studied charge recombination, remains somewhat limited. This limitation stems from the inherently heterogeneous nature of traps at both temporal and spatial scales, which renders the characterization of charge trapping a formidable challenge. Fortunately, recent advancements in both time-resolved spectroscopy and space-resolved microscopy have paved the way for considerable progress in the investigation and manipulation of charge trapping. In this Perspective, we focus on charge trapping in photocatalysts with the aim of establishing a direct link to their photocatalytic activities. To achieve this, we begin by elucidating the principles of advanced time-resolved spectroscopic techniques such as femtosecond time-resolved transient absorption spectroscopy and space-resolved microscopic methods, such as single-molecule fluorescence microscopy and surface photovoltage microscopy. Additionally, we provide an overview of noteworthy research endeavors dedicated to probing charge trapping using time- and space-resolved techniques. Our attention is then directed toward recent achievements in the manipulation of charge trapping in photocatalysts through defect engineering. Finally, we summarize this Perspective and discuss the future challenges and opportunities that lie ahead in the field.

Time-Resolved Spectroscopy for Dynamic Investigation of Photoresponsive Metal-Organic Frameworks.

Photoresponsive MOFs with precise and adjustable reticular structures are attractive for light conversion applications. Uncovering the photoinduced carrier dynamics lays the essential foundation for the further development and optimization of the MOF material. With the application of time-resolved spectroscopy, photophysical processes including excimer formation, energy transfer/migration, and charge transfer/separation have been widely investigated. However, the identification of distinct photophysical processes in real experimental MOF spectra still remains difficult due to the spectral and dynamic complexity of MOFs. In this Perspective, we summarize the typical spectral features of these photophysical processes and the related analysis methods for dynamic studies performed by time-resolved photoluminescence (TR-PL) and transient absorption (TA) spectroscopy. Based on the recent understanding of excited-state properties of photoresponsive MOFs and the discussion of challenges and future outlooks, this Perspective aims to provide convenience for MOF kinetic analysis and contribute to the further development of photoresponsive MOF material.

Site-Directed Mutagenesis of the Chlorophyll-Binding Sites Modulates Excited-State Lifetime and Chlorophyll-Xanthophyll Energy Transfer in the Monomeric Light-Harvesting Complex CP29.

We combine site-directed mutagenesis with picosecond time-resolved fluorescence and femtosecond transient absorption (TA) spectroscopies to identify excitation energy transfer (EET) processes between chlorophylls (Chls) and xanthophylls (Xant) in the minor antenna complex CP29 assembled inside nanodiscs, which result in quenching. When compared to WT CP29, a longer lifetime was observed in the A2 mutant, missing Chl a612, which closely interacts with Xant Lutein in site L1. Conversely, a shorter lifetime was obtained in the A5 mutant, in which the interaction between Chl a603 and Chl a609 is strengthened, shifting absorption to lower energy and enhancing Chl-Xant EET. Global analysis of TA data indicated that EET from Chl a Qy to a Car dark state S* is active in both the A2 and A5 mutants and that their rate constants are modulated by mutations. Our study provides experimental evidence that multiple Chl-Xant interactions are involved in the quenching activity of CP29.

Solid-State Emissive meso-Aryl/Alkyl-Substituted and Heteroatom-Mixed BOPPY Dyes: Syntheses, Structures, Physicochemical, Redox Properties, and Computational Analysis.

A series of solid-state emissive meso-aryl/alkyl-substituted and heteroatom-mixed bisBF2-anchoring fluorophore incorporating pyrrolyl-pyridylhydrazone (BOPPY) dyes have been developed by a one-pot condensation of ketonized or formylated pyrroles and 2-heterocyclohydrazine as well as the subsequent borylation coordination. Interestingly, the BOPPY dyes with meso-alkyl-substituted groups or oxygen-substituted pyridine moieties exhibit high fluorescence quantum yields (QYs) of up to 79%, the highest solid QY of 74%, and long lifetimes independent of polarity in the available BOPPYs. On the other hand, the BOPPYs with meso-aryl or N-substituted moieties display a high solution QY of up to 93% and slight emission wavelength maxima. However, the S-substituted BOPPY dye exhibited weak fluorescence in all studied solvents, which was attributed to the structural flexibility of the N-C-S bond and different from those BOPPYs with O or N substitution, indicated by quantum calculations. And the significant excited-state structural rearrangement in a polar solvent is further confirmed by femtosecond time-resolved transient absorption spectroscopy. More importantly, those novel and barely fluorescent BOPPYs in acetonitrile show advantageous aggregation-induced enhanced emission and viscosity-dependent activities. These advancements in the photophysical and electrochemical properties of BOPPY dyes offer valuable insights into their further development and potential applications.

In-situ and operando Grazing Incidence XAS: a novel set-up and its application to model Pd electrodes for alcohols oxidation

Abstract In this article, we present an in-situ and operando time-resolved X-ray Absorption Spectroscopy (XAS) technique which exploits a combination of Grazing Incidence XAS (GIXAS) and Fixed Energy X-ray Absorption Voltammetry (FEXRAV), the Grazing Incidence FEXRAV (GI-FEXRAV). A case-study is also outlined. Palladium ultra-low loadings were deposited above Au polycrystalline iso-oriented substrates adopting three different deposition methods: surface-controlled electrochemical methods, direct electrodeposition, and physical vapour deposition (PVD). These catalytical surfaces were prepared for the investigation by GI-FEXRAV of the Pd oxidation/dissolution phenomenon that could occur when the metal is used in the anodic compartment of Direct Alcohol Fuel Cells (DAFCs) or in electrochemical reformers. Moreover, we report a robust, low cost and versatile procedure to obtain wide and flat iso-oriented gold substrates that can mimic monocrystalline gold (1 1 1) in the electrochemical response. The use of GI-FEXRAV for the operando characterization of the catalysts, in conjunction with the designed experimental cell and our flexible Au-based electrochemical substrates show an invaluable potential in the operando study of fundamental phenomena in heterogeneous electrocatalysis model systems and, due to its versatility, paves the way to further studies on a wide selection of electrochemical systems.

Difference of carrier dynamics in a semiconductor saturable absorber mirror with and without B+ ion-implantation.

Three samples whose growth temperatures were 450°C, 500°C, and 560°C for S E S A M 1, S E S A M 2, and S E S A M 3, respectively, were tested by femto-second time-resolved transient absorption spectroscopy. The results indicate that the carrier dynamics of excited state absorption were dominant, and the lifetimes of carriers trapped by defect levels were about tens of pico-seconds. To further study the influence of carrier dynamics and recovery time of samples by ion-implantation, B + ions of 80 and 130 KeV were implanted into the samples with dose of 1014/c m 2. The modified samples showed a dominance of ultra-fast carrier dynamics of ground-state bleaching and direct recombination, which lasted for hundreds of femto-seconds, over excited state absorption. Additionally, carrier fast trapping was observed to be competitive with the excited state absorption process. After ion-implantation, the carrier dynamics of carrier trapping were enhanced, which contributed to forming an ultra-short laser, while the carrier dynamics of absorption of the excited state were suppressed. The conclusion that defect levels were partially eliminated by B + ion-implantation can be drawn.