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At least 919 records · Page 51

Effect of growth dynamics on the structural, photophysical and pseudocapacitance properties of famatinite copper antimony sulphide colloidal nanostructures (including nanosheets)

Facile phase selective synthesis of copper antimony sulphide (CAS) nanostructures is important because of their tunable photoconductive and electrochemical properties. In this study, off-stoichiometric famatinite phase CAS (fCAS) quasi-spherical and quasi-hexagonal colloidal nanostructures (including nanosheets) of sizes, 2.4–18.0 nm were grown under variable conditions of temperature (60–200 °C), time and oleylamine capping ligand concentration using copper(II) acetylacetonate and antimony(III) diethyldithiocarbamate precursors. Data from powder X-ray diffraction, Raman spectroscopy and high-resolution scanning/transmission electron microscopy confirm the tetragonal structure of the famatinite phase. X-ray photoelectron spectroscopy, transmission electron microscopy and scanning electron microscopy-energy dispersive X-ray spectroscopy data suggest a correlation of particle size, morphology and composition of the off-stoichiometric fCAS nanostructures with growth temperature and time, and oleylamine concentration. The off-stoichiometric Cu 3-a Sb 1+b S 4±c (a, b, c – mole fractions) nanostructures being severely copper-deficient and antimony-rich, exhibit shallow-lying acceptor copper vacancy states, deep-lying donor states of antimony interstitials, sulphur vacancies and antimony-copper antisites and shallow-lying acceptor surface trapping states. Further, these electronic states are likely implicated in tunable UV-visible absorption and bandgaps between 2.3 and 2.8 eV, and broad visible-NIR photoluminescence with fast recombination of radiative lifetimes between 0.2 and 6.2 ns, confirmed from absorption, steady-state and time-resolved photoluminescence spectroscopies. Additionally, cyclic voltammetry and electrochemical impedance spectroscopy confirm that electrodes of the fCAS nanostructures display slightly variable pseudocapacitance of charge-storage primarily via possible sodium ion intercalation with a high specific capacitance of ~84 F g -1 obtained at a scan rate of 5 mV s -1 . Overall, these results show the influence of composition, in particular point defects, phase quality and morphology on the optical and pseudocapacitance properties of fCAS nanostructures, suitable as solar absorbers or electrodes for energy storage devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sub-100-fs energy transfer in coenzyme NADH is a coherent process assisted by a charge-transfer state

Excitation energy transfer (EET) is a key photoinduced process in biological chromophoric assemblies. Here we investigate the factors which can drive EET into efficient ultrafast sub-ps regimes. We demonstrate how a coherent transport of electronic population could facilitate this in water solvated NADH coenzyme and uncover the role of an intermediate dark charge-transfer state. High temporal resolution ultrafast optical spectroscopy gives a 54 ± 11 fs time constant for the EET process. Nonadiabatic quantum dynamical simulations computed through the time-evolution of multidimensional wavepackets suggest that the population transfer is mediated by photoexcited molecular vibrations due to strong coupling between the electronic states. The polar aqueous solvent environment leads to the active participation of a dark charge transfer state, accelerating the vibronically coherent EET process in favorably stacked conformers and solvent cavities. Our work demonstrates how the interplay of structural and environmental factors leads to diverse pathways for the EET process in flexible heterodimers and provides general insights relevant for coherent EET processes in stacked multichromophoric aggregates like DNA strands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modified Fermi’s golden rule rate expressions

Fermi’s golden rule (FGR) serves as the basis for many expressions of spectroscopic observables and quantum transition rates. The utility of FGR has been demonstrated through decades of experimental confirmation. However, there still remain important cases where the evaluation of a FGR rate is ambiguous or ill-defined. Examples are cases where the rate has divergent terms due to the sparsity in the density of final states or time dependent fluctuations of system Hamiltonians. Strictly speaking, assumptions of FGR are no longer valid for such cases. However, it is still possible to define modified FGR rate expressions that are useful as effective rates. The resulting modified FGR rate expressions resolve a long standing ambiguity often encountered in using FGR and offer more reliable ways to model general rate processes. Finally, simple model calculations illustrate the utility and implications of new rate expressions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nonlinear Scaling of Water–Ion Interactions and Dynamics in Alkaline Solutions

Water-ion interactions govern many solvent properties critical to solution-phase chemistry and the behavior of liquid water. The water-ion interactions in alkaline conditions were probed using two-dimensional infrared spectroscopy (2D IR), small-angle x-ray scattering (SAXS), and nuclear magnetic resonance spectroscopy (NMR). Energy transfer between the donor molecule KSeCN, used as a 2D IR probe, and the acceptor molecule NaOD was used to track the average separation distance of ions in a D 2 O solution, while SAXS measurements showed effects in the bulk D 2 O solvent. Here, we observe consistent nonlinear scaling in the SeCN - and OD - average separation distance as a function of NaOD concentration while bulk solution D 2 O-to-D 2 O average separation distance remained highly linear. Ultrafast measurements of solution dynamics via 2D IR and polarization-selective pump-probe spectroscopy show consistent scaling in correlation times as a function of concentration. These results suggests that the SeCN - and OD - anions participate in a water-ion network that significantly reduces the degrees of freedom for the distribution of ions in solution below the standard stochastic for ion distribution.

2D IR Spectroscopy↗

Broadband Rotational Spectroscopy in Uniform Supersonic Flows: Chirped Pulse/Uniform Flow for Reaction Dynamics and Low Temperature Kinetics

ConspectusThe study of gas-phase chemical reactions at very low temperatures first became possible with the development and implementation of the CRESU (French acronym for Reaction Kinetics in Uniform Supersonic Flows) technique. CRESU relies on a uniform supersonic flow produced by expansion of a gas through a Laval (convergent-divergent) nozzle to produce a wall-less reactor at temperatures from 10 to 200 K and densities of 1016-1018 cm-3 for the study of low temperature kinetics, with particular application to astrochemistry. In recent years, we have combined uniform flows with revolutionary advances in broadband rotational spectroscopy to yield an instrument that affords near-universal detection for novel applications in photodissociation, reaction dynamics, and kinetics. This combination of uniform supersonic flows with chirped-pulse Fourier-transform microwave spectroscopy (Chirped-Pulse/Uniform Flow, CPUF) permits detection of any species with a modest dipole moment, thermalized to the uniform temperature of the gas flow, with isomer, conformer, and vibrational state specificity. In addition, the use of broadband, high-resolution, and time-dependent (microsecond time scale) micro- and mm-wave spectroscopy makes it an ideal tool for characterizing both transient and stable molecules, as well as studying their spectroscopy and dynamics.In this Account, we review recent advances made using the CPUF technique, including studies of photodissociation, radical-radical reaction dynamics, and low temperature kinetics. These studies highlight both the strength of universal and multiplexed detection and the challenges of coupling it to a high-density collisional environment. Product branching and product evolution as a function of time have been measured for astrochemically relevant systems, relying on the detailed characterization of these flow conditions via experiments and fluid dynamics simulations. In the photodissociation of isoxazole, an unusual heterocyclic molecule with a very low-energy conical intersection, we have identified 7 products in 5 reaction channels and determined the product branching, pointing to both direct and indirect pathways. We have also approached the same system from separated NO and C3H3 reactants to explore a broader range of the potential energy surface, demonstrating the power of multichannel branching measurements for complex radical-radical reactions. We determined the product branching in the C3H2 isomers in the photodissociation of the propargyl radical and identified the importance of a hydrogen atom catalyzed isomerization to the lowest energy cyclic form. This then motivated a study of direct D-H exchange reaction in radicals, in which we demonstrate that it is an important and overlooked pathway for deuterium fractionation in astrochemical environments. Recently, we have shown the measurement of low temperature kinetics inside an extended Laval nozzle, after which a shock-free secondary expansion to low temperature and density affords an ideal environment for detection by rotational spectroscopy. These results highlight the power and potential of the CPUF approach, and future prospects will also be discussed in light of these developments.

Dias, Nureshan↗

A practical approach for identifying various polarization behaviors of redox-stable electrodes in symmetrical solid oxide fuel cells

In symmetrical solid oxide fuel cells, comprehensively understanding the elementary reaction processes and the polarization behaviors of redox-stable electrode materials is critical for further optimization of the electrode performance. In this work, a systematical and practical approach, based on electrochemical impedance spectroscopy technology, is applied to identify the rate-limiting elementary reactions of the redox-stable electrodes. The feasibility of this proposed method is demonstrated in symmetrical solid oxide fuel cells with Sr 2 Fe 1.5 Mo 0.5 O 6-σ -Ce 0.9 Gd 0.1 O 1.95 as electrodes. Based on the characteristic frequency ranges and the experimental results tested under various fuel gas components, operating temperatures, and discharge current densities, the rate-limiting steps of the cathode are associated with the formation of adsorbed oxygen ions and the combination of oxygen ions and oxygen vacancies, while the rate-limiting steps of the anode are ascribed to the hydrogen dissociated adsorption and the steam desorption processes. This experimental and analysis framework can be straightforwardly extended to other electrode materials to unravel their electrochemical performance in detail.

25 ENERGY STORAGE↗

Multimodal Ambient Pressure Sample Environment for the HIPPIE Solid-Gas Endstation at MAX IV Laboratory

The HIPPIE APXPS instruments have undergone several major upgrades, such as developing a dedicated solid gas endstation to specialize in multimodal ambient pressure sample environments centered around X-ray photoelectron spectroscopy. Herein, the technical specifications of the HIPPIE solid gas endstation are detailed; upgrades to the laser heating and gas systems, as well as the addition of an offline 1 bar reactor, are introduced. To demonstrate how the endstation is currently being utilized, scientific examples of all upgrades are presented, as well as science cases using infrared reflection-adsorption spectroscopy. The HIPPIE solid gas endstation is maturing into an instrument offering bespoke sample environments aimed at pushing experimental capabilities, especially in the time-resolved domain.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electron Transfer Going the Distance: Mn-Doped ZnSe as a Model Photocatalytic System

In this work, time-resolved photoluminescence and transient absorption spectroscopy are used to examine the influence that long excited state lifetimes of Mn-doped nanocrystals have on the mechanisms of photo-induced electron transfer (PET) in photocatalytic systems. Mn-doped ZnSe nanocrystals can undergo PET over their nearly millisecond excited state lifetime, which enables electron transfer to viologens in solution over large encounter distances in comparison to molecular length scales. The long excited state lifetimes also enable diffusion of the excited nanocrystals over hundreds of nanometers in solution, allowing them to react with molecular species at nanomolar concentrations. The ability to capture and sustain optical energy in spin-forbidden transitions among crystal field states of the Mn ions opens opportunities to explore the influence that long excited state lifetimes have on photocatalytic reaction mechanisms involving molecular species such as CO 2 that can be difficult to concentrate or attach to nanocrystal surfaces.

14 SOLAR ENERGY↗

Rotational coherence dominates early-time dynamics and produces long-time revivals in the S 2 state of azulene

Here, the ultrafast dynamics of azulene have been debated for decades, with reported picosecond decay constants variously attributed to intramolecular vibrational redistribution (IVR), internal conversion, or rotational dephasing. Using polarization- and femtosecond time-resolved resonance-enhanced multiphoton ionization spectroscopy with a nanosecond delay window, we disentangle this long-standing inconsistency and show that the early 2–5 ps decay component arises entirely from the rotational dephasing of an excited-state wavepacket. Identical time constants extracted from the decay of the parallel signal and the rise of the perpendicular signal across multiple vibronic origins provide an unambiguous rotational anisotropy signature, eliminating the need for IVR-based interpretations. Extending the measurement window to 1.3 ns reveals well-structured J-type and C-type rotational coherence revivals in S 2 azulene on top of the well-documented fluorescence decay, demonstrating that both the short- and long-time dynamics contain information about the coherent rotational dynamics. These results show that azulene, and by extension polycyclic aromatic hydrocarbons, can sustain structured rotational coherence deep into the nanosecond regime, positioning PAHs as model systems for quantum-coherent wavepacket dynamics and providing a framework for probing coherence, decoherence, and rotational control in electronically rich molecular systems.

Zhan, Jie [University of Georgia, Athens, GA (Unit↗

Distinguishing Electron and Hole Dynamics in Functionalized CdSe/CdS Core/Shell Quantum Dots Using Complementary Ultrafast Spectroscopies and Kinetic Modeling

The evolution of excitation energy and photogenerated charges in semiconductor quantum dots (QDs) functionalized with molecular acceptors can be probed on ultrafast time scales using techniques such as transient absorption (TA) spectroscopy. However, historical interpretations that the 1S(e)-1S 3/2 (h) transition in Cd-chalcogenide QDs is fully attributable to electrons may be misleading, and multiexponential models used to fit TA kinetics do not correspond directly to specific photophysical processes. Here, we present visible-wavelength and mid-IR TA and time-resolved photoluminescence measurements to inform a comprehensive kinetic model of the photoexcited CdSe/CdS core/shell QDs functionalized with passivating oleic acid (OA), hole-accepting ferrocene, or electron-accepting naphthalene bisimide (NBI). We show that ~30% of the 1S signal and 72% of the IR signal can originate from holes in well-passivated core/shell QDs. We also demonstrate evidence of electron trapping in OA-capped core/shell QDs, with additional electron transfer and hole trapping in the QDs functionalized with NBI. Electron (hole) trapping and detrapping occur in 450 ± 100 ps (430 ± 70 ps) and 340 ± 100 ps (1.1 ± 0.4 ns) respectively, while the time constant for electron transfer to NBI is ~1.8 ns. The comprehensive picture of photophysical processes provided by the complementary ultrafast techniques and kinetic modeling can accelerate both the fundamental science and application development of nanostructured and molecular systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Laser-Assisted Synthesis of Monolayer 2D MoSe 2 Crystals with Tunable Vacancy Concentrations: Implications for Gas and Biosensing

We report tuning the structural and electronic properties of atomically thin two-dimensional (2D) materials via defect and vacancy engineering is the key to enabling their potential use in various applications, including electronics, energy, and sensing devices. Vacancies are, for instance, becoming highly promising for the enhanced interaction of gases and biomolecules with 2D materials in energy and sensing applications. However, the deterministic generation of desirable vacancies with tunable concentrations remains a challenge in 2D materials due to the limitations in the current growth methods, such as the complex reaction chemistries and gas flow dynamics. Therefore, engineering defects and vacancies in 2D materials have been mainly limited to destructive top-down processes such as heating, ion bombardments, and laser postprocessing. Here, we introduce a single-step bottom-up synthesis approach for the growth of monolayer MoSe 2 crystals with tunable vacancy concentrations. This method utilizes the spatiotemporal properties and adjustable power densities of the lasers to control the vaporization dynamics of the stoichiometric MoSe 2 powders. Such a mechanism in the vaporization allows us to grow tunable stoichiometry monolayer MoSe 2–x crystals on the substrates. The localized and time-controlled (250 ms to 2 s) vaporization of the MoSe 2 powder by a CO 2 laser enables the formation of monolayer crystals with controlled vacancy concentrations ranging from ~1 to 20%. The effects of laser power, laser irradiation time, and background pressure on the tuning range and subsequent properties of the crystals are investigated and quantified using Raman and photoluminescence spectroscopy, scanning transmission electron microscopy (STEM), and time-correlated single-photon counting (TCSPC). This bottom-up synthesis is a promising approach that allows the deterministic vacancy tuning for future electronics and, in particular, gas and biosensing applications without the need for further postprocessing and potential structural disruption of the crystals.

2D materials↗

Physics-Based Real-time Analysis and Control to Achieve Transient-Free Operations for the ITER Era (Final Report)

This is the final report for the early career award for Prof. Egemen Kolemen that aimed to develop the physics and technical basis of real-time transient – i.e. disruptions and Edge Localized Modes (ELMs) – avoidance and feedback control at the DIII-D nuclear fusion facility for the ITER era. During this project, we reconstructed high quality real-time DIII-D equilibria using kinetic information from the motional Stark effect (MSE), Thomson Scattering (TS), and Charge Exchange Recombination (CER) spectroscopy. These equilibria were analyzed in real-time to determine the low-n ideal MHD stability and the pedestal stability thresholds, and to obtain plasma response models. These calculations were used to understand which physical process evolves to lead to the onset of disruption in ITER-relevant scenarios at DIII-D, and how disruption can be predicted using stability analysis as opposed to the current methods of correlation of various signals, which are descriptive but lack predictive power. In the disruption studies, we focused on tearing modes, since these constitute the vast majority of disruptions in this regime. With this knowledge, real-time disruption avoidance algorithms were developed and tested. The enhanced situation awareness and physics insight were used in advanced real-time feedback control of pedestal and core profiles, which allowed the pursuit and sustainment of transient-free high-confinement regimes that cannot be achieved via feed-forward design based on in-between shot analysis.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Insights from Femtosecond Transient Absorption Spectroscopy into the Structure–Function Relationship of Glyceline Deep Eutectic Solvents

This study aimed to determine the structure–function relationship (SFR) for ChCl–glycerol mixtures, a deep eutectic solvent (DES), by investigating their microscopic solvation dynamics and how it relates to their macroscopic properties across varying concentrations of ChCl. Femtosecond transient absorption (fs-TA) spectroscopy revealed two distinct solvation dynamics time constants: τ 1 , governed by glycerol–glycerol interactions, and τ 2 , dominated by the choline response. The τ 2 minimum at 25–30 mol % ChCl closely aligned with the eutectic composition (~33.33 mol % ChCl), where the glycerol network was the most organized and the choline ions exhibited the fastest relaxation. The viscosity decreased sharply up to ~25 mol % ChCl and then plateaued, while the conductivity increased monotonically with ChCl concentration, reflecting enhanced ionic mobility. The density decreased with both increasing ChCl concentration and temperature, indicating disrupted hydrogen bonding and reduced molecular packing. The polarity, measured using betaine-30 (B30) and the E T (30) polarity scale, increased steeply up to approximately 25 mol % ChCl before reaching a plateau. These findings identified the eutectic composition as the optimal concentration range for balancing stability, fluidity, conductivity, and enhanced dynamics within the glycerol system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Roadmap on quantum light spectroscopy

Conventional spectroscopy uses classical light to detect matter properties through the variation of its response with frequencies or time delays. Quantum light opens up new avenues for spectroscopy by utilizing parameters of the quantum state of light as novel control knobs and through the variation of photon statistics by coupling to matter. This Roadmap article focuses on using quantum light as a powerful sensing and spectroscopic tool to reveal novel information about complex molecules that is not accessible by classical light. It aims at bridging the quantum optics and spectroscopy communities which normally have opposite goals: manipulating complex light states with simple matter e.g. qubits versus studying complex molecules with simple classical light, respectively. Here, articles cover advances in the generation and manipulation of state-of-the-art quantum light sources along with applications to sensing, spectroscopy, imaging and interferometry.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Time-resolved observation of transient precursor state of CO on Ru(0001) using carbon K-edge spectroscopy

The transient dynamics of carbon monoxide (CO) molecules on a Ru(0001) surface following femtosecond optical laser pump excitation has been studied by monitoring changes in the unoccupied electronic structure using an ultrafast X-ray free-electron laser (FEL) probe. The particular symmetry of perpendicularly chemisorbed CO on the surface is exploited to investigate how the molecular orientation changes with time by varying the polarization of the FEL pulses. The time evolution of spectral features corresponding to the desorption precursor state was well distinguished due to the narrow line-width of the C K-edge in the X-ray absorption (XA) spectrum, illustrating that CO molecules in the precursor state rotated freely and resided on the surface for several picoseconds. Most of the CO molecules trapped in the precursor state ultimately cooled back down to the chemisorbed state, while we estimate that ~14.5 ± 4.9% of the molecules in the precursor state desorbed into the gas phase. Finally, it was also observed that chemisorbed CO molecules diffused over the metal surface from on-top sites toward highly coordinated sites. In addition, a new “vibrationally hot precursor” state was identified in the polarization-dependent XA spectra.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Absolute 1* quantum yields for the ICN A state by diode laser gain versus absorption spectroscopy

Absolute I* quantum yields were measured as a function of wavelength for room temperature photodissociation of the ICN A state continuum. The temperature yields are obtained by the technique of time-resolved diode laser gain-versus-absorption spectroscopy. Quantum yields are evaluated at seven wavelengths from 248 to 284 nm. The yield at 266 nm is 66.0 +/- 2% and it falls off to 53.4 +/- 2% and 44.0 +/- 4% at 284 and 248 respectively. The latter values are significantly higher than those obtained by previous workers using infrared fluorescence. Estimates of I* quantum yields obtained from analysis of CN photofragment rotational distributions, as discussed by other workers, are in good agreement with the I* yields. The results are considered in conjunction with recent theoretical and experimental work on the CN rotational distributions and with previous I* yield results.

Hess, Wayne P.↗

A variant of the MenB strain of Synechocystis sp. PCC 6803 disrupts a stress response pathway allowing DMPBQ to occupy the A 1 sites of photosystem I

Phylloquinone (PhQ) plays a unique role in photosynthesis as the A1A and A1B intermediates in light-driven electron transfer in Photosystem I (PSI). When PhQ biosynthesis is inhibited by deletion of the menB gene in the cyanobacterium Synechocystis sp. PCC 6803, previous studies have shown that plastoquinone-9 (PQ-9) occupies the A 1 sites. However, a recent cryo-electron microscopy structure of a strain of ΔmenB from the year 2023 revealed an unusual quinone in the A 1 sites with a benzoquinone headgroup similar to PQ-9 and a phytyl tail similar to PhQ. Here, we investigate its biosynthesis and binding properties. Mass spectrometry confirms that PSI from the 2023 ΔmenB strain contains 2,3-dimethyl-5-phytyl-1,4-benzoquinone (DMPBQ), while PSI from the original strain contains PQ-9. Whole genome sequencing reveals that a mutation in slr1737 (tocopherol cyclase) leads to the accumulation of DMPBQ, an intermediate in the tocopherol biosynthetic pathway. Transient optical and electron paramagnetic resonance spectroscopy studies show that when DMPBQ occupies the A 1 sites, it does not exchange with exogenously supplied PhQ in contrast to PQ-9, which exchanges readily. We propose that the slr1737 mutation in the 2023 ΔmenB strain is a likely candidate for the source of the phenotype. This new strain has sacrificed tocopherol synthesis, the absence of which is known to have no effect on growth under low stress conditions, resulting in incorporation of DMPBQ in the A 1 sites. The tighter binding and function of DMPBQ likely allow this ΔmenB strain to outcompete its peers under optimal growth conditions and thus dominate the population.

2,3-dimethyl-5-phytyl-1,4-benzoquinone↗

Holistic digital gamma-ray spectroscopy methods and instrumentation for high-throughput high-resolution applications

Method of real-time adaptive digital pulse signal processing for high count rate gamma-ray spectroscopy applications includes receiving a preamplifier signal at a pulse deconvolver, the preamplifier signal including resolution deterioration resulting from pulse pile-up. The method further includes generating a deconvoluted signal, by the pulse deconvolver, from the preamplifier signal, the deconvoluted signal having less resolution deterioration as compared to the received preamplifier signal. The method furthermore includes shaping of the deconvoluted signal by a trapezoid filter, the shaping comprising adjusting a shaping parameter of the trapezoid filter for an incoming signal based on a time separation from a subsequent incoming signal.

Hawari, Ayman I.↗