Time-dependent Emission Research Articles

Light-Operated Diverse Logic Gates Enabled by Modulating Time-Dependent Fluorescence of Dissipative Self-Assemblies.

Light-fueled dissipative self-assembly possesses enormous potential in the field of optical information due to controllable time-dependent optical signals, but remains a great challenge for constructing intelligent light-operated logic circuits due to the limited availability of optical signal inputs and outputs. Herein, a series of light-fueled dissipative self-assembly systems with variable optical signals are reported to realize diverse logic gates by modulating time-dependent fluorescence variations of the loaded fluorophores. Three kinds of alkyl trimethylammonium homologs are employed to co-assemble with a merocyanine-based photoinduced amphiphile separately to construct a series of dissipative self-assemblies, showing unexpectedly different fluorescence control behaviors of loaded fluorophores during light irradiation and thermal relaxation processes. The opposite monotonicity of time-dependent emission intensity is achieved just by changing the excitation wavelength. Furthermore, by varying the types of trimethylammoniums and excitation wavelengths, a robust logic system is accomplished, integrating AND, XNOR, and XOR functions, which provides an effective pathway for advancing information transmission applications.

Structured Jet Model for Multiwavelength Observations of the Jetted Tidal Disruption Event AT 2022cmc

AT 2022cmc is a recently documented tidal disruption event that exhibits a luminous jet, accompanied by fast-declining X-ray and long-lasting radio and millimeter emission. Motivated by the distinct spectral and temporal signatures between the X-ray and radio observations, we propose a multizone model involving relativistic jets with different Lorentz factors. We systematically study the evolution of faster and slower jets in an external density profile, considering the continuous energy injection rate associated with time-dependent accretion rates before and after the mass fallback time. We investigate time-dependent multiwavelength emission from both the forward shock (FS) and reverse shock (RS) regions of the fast and slow jets, in a self-consistent manner. Our analysis demonstrates that the energy injection rate can significantly impact the jet evolution and subsequently influence the lightcurves. We find that the X-ray spectra and lightcurves could be described by electron synchrotron emission from the RS of the faster jet, in which the late-time X-ray upper limits, extending to 400 days after the disruption, could be interpreted as a jet break. Meanwhile, the radio observations can be interpreted as a result of synchrotron emission from the FS region of the slower jet. We also discuss prospects for testing the model with current and future observations.

Reversible Multi-Color optical switch utilizing tetraphenylethylene and spiropyran Complexes: Applications in advanced information encryption

In this paper, we introduced a strategic methodology to obtain time-resolved encryption utilizing a new technique. This method utilizes a reversible supramolecular optical switch, which is based on complexes consisting of tetraphenylethylene and spiropyran. Notably, these components are separately attached at the focal point of the same cholesterol-based unit, wherein the cholesterol-based unit can provide the essential driving forces to form complexes. A series of complexes were prepared with varying molar ratios (TPE/SP), allowing for the tuning of fluorescence emission. The supramolecular system leverages hydrogen bonding, van der Waals forces, and other non-covalent interactions to orchestrate the collaboration between the fluorophores (tetraphenylethylene) and the photochromic molecule (spiropyran). This coordination results in exceptional photochromic attributes, including rapid response, high contrast, and the capability to regulate fluorescence. The system is capable of achieving tunable dynamic fluorescence emission that transitions from brilliant blue to light purple and finally to red through fluorescence resonance energy transfer (FRET) after successive irradiation periods. Additionally, by fine-tuning the ratio of tetraphenylethylene to spiropyran, different dynamic fluorescence emission can be precisely manipulated. It is rarely reported that complexes accomplish time-dependent fluorescence emission with high-contrast. We are confident that the complexes, grounded on cholesterol unit, hold promise for broader applicability in developing innovative time-dependent fluorescent materials. Such materials can be effectively utilized for time-dependent information encryption, thereby bolstering security measures against unauthorized access.

Applied radiation tags for warhead dismantlement transparency

This study explores the feasibility of applying radiation tags as a Chain of Custody tool to confirm the dismantlement of individual warheads by investigating time dependent emissions from special nuclear material. Precedents of photon and neutron sources that have been used to irradiate warhead components are presented. Measurements of irradiated Highly Enriched Uranium (HEU) are used to benchmark simulations with the CINDER90 depletion code module within MCNP. Delayed gamma emissions are simulated as a function of time since irradiation of moderated HEU and Weapons Grade Plutonium with photon and neutron sources. Models of commercial 9 MV and 15 MV linacs were found to induce ∼109fissions/g and ∼1011fissions/g, respectively, creating 3 to 4 orders of magnitude more delayed gammas than neutron sources, modeled at 1010n/s. However, a DT neutron source was found to induce sufficient fissions, ∼107fissions/g, to create quantifiable signatures relative to intrinsic emissions. Applied radiation tagging is determined to be technically feasible, but its operational context and practical implementation requires significant development.

Modeling of the Time-Dependent H2 Emission and Equilibrium Time in H2-Enriched Polymers with Cylindrical, Spherical and Sheet Shapes and Comparisons with Experimental Investigations.

Time-dependent emitted H2 content modeling via a reliable diffusion analysis program was performed for H2-enriched polymers under high pressure. Here, the emitted hydrogen concentration versus elapsed time was obtained at different diffusivities and volume dimensions for cylinder-, sphere- and sheet-shaped specimens. The desorption equilibrium time, defined as the time when the H2 emission content is nearly saturated, was an essential factor for determining the periodic cyclic testing and high-pressure H2 exposure effect. The equilibrium time in the desorption process was modeled. The equilibrium time revealed an exponential growth behavior with respect to the squared thickness and the squared diameter of the cylinder--shaped specimen, while it was proportional to the squared diameter for the sphere-shaped specimen and to the squared thickness for the sheet-shaped specimen. Linear relationships between the reciprocal equilibrium time and diffusivity were found for all shaped polymers. The modeling results were confirmed by analysis of the solutions using Fick's second diffusion law and were consistent with the experimental investigations. Numerical modeling provides a useful tool for predicting the time-dependent emitted H2 behavior and desorption equilibrium time. With a known diffusivity, a complicated time-dependent emitted H2 behavior with a multi-exponential form of an infinite series could also be predicted for the three shaped samples using a diffusion analysis program.

Time-variable diffuse γ-ray foreground

ABSTRACT While the data analysis of γ-ray telescopes has now become more robust, some signals may be misinterpretations of a time-variable foreground emission from the Solar system, induced by low-energy cosmic-ray interactions with asteroids. Our goal is to provide emission templates for this time-variable diffuse γ-ray foreground by considering the populations of Main Belt Asteroids, Jovian and Neptunian Trojans, Kuiper Belt Objects, and the Oort Cloud. We model the spatial distribution of all known asteroids by performing 3D-fits to determine their density profiles and calculate their appearances by line-of-sight integrations. Because Earth and the asteroids are moving with respect to each other, we obtain diffuse emission templates varying on time-scales of days to decades. We find that the temporal variability can lead to flux enhancements that may mimic emission features unless properly taken into account. This variation is further enhanced by the Solar cycle as the cosmic-ray spectrum is attenuated by the Solar modulation potential, leading to a relative flux increase of the outer asteroids. The cumulative effect of the time-dependent emission is illustrated for the case of the ‘511 keV OSSE fountain’, and for emission features near the Galactic Centre, both being possible misinterpretations of the Solar system albedo. We recommend that γ-ray data analyses should always take into account the possibility of a time-variable foreground. Due to the ecliptic overlap with the Galactic plane, the Galactic emission is expected to be weaker by 0.1–20 per cent, depending on time (relative planetary motion), energy, and Solar cycle, which has consequences for the interpretation of dark matter annihilation cross sections, cosmic-ray spectra and amplitudes, as well as nucleosynthesis yields and related parameters.

Laser ablation fingerprint in low crystalline carbon nanotubes: A structural and photothermal analysis

Carbon nanotubes (CNT) hold promise as photothermal materials due to their cost-effectiveness, stability, and broad optical absorbance. Here, we investigate the structural and morphological modifications in low-crystalline vertically aligned CNT synthetized via chemical vapor deposition on n-type Si substrates at 750 °C, followed by annealing treatment with near-infrared laser radiation. Raman spectroscopy revealed laser-induced amorphous regions, facilitating identification of ablation thresholds. Time-dependent nonlinear photothermal emission, associated with CNT ablation, showed a stable thermodynamic equilibrium with broad-band radiation from an electron-hole plasma. We propose a model based on Raman spectra and positional scans of the ablation fingerprint, enabling correlation with the beam temperature profile. This study offers insights into laser beam characterization, with potential applications in plasma and optics disciplines.

Structure-changeable luminescent Eu(III) complex as a human cancer grade probing system for brain tumor diagnosis.

Accurate determination of human tumor malignancy is important for choosing efficient and safe therapies. Bioimaging technologies based on luminescent molecules are widely used to localize and distinguish active tumor cells. Here, we report a human cancer grade probing system (GPS) using a water-soluble and structure-changeable Eu(III) complex for the continuous detection of early human brain tumors of different malignancy grades. Time-dependent emission spectra of the Eu(III) complexes in various types of tumor cells were recorded. The radiative rate constants (kr), which depend on the geometry of the Eu(III) complex, were calculated from the emission spectra. The tendency of the kr values to vary depended on the tumor cells at different malignancy grades. Between T = 0 and T = 3h of invasion, the kr values exhibited an increase of 4% in NHA/TS (benign grade II gliomas), 7% in NHA/TSR (malignant grade III gliomas), and 27% in NHA/TSRA (malignant grade IV gliomas). Tumor cells with high-grade malignancy exhibited a rapid upward trend in kr values. The cancer GPS employs Eu(III) emissions to provide a new diagnostic method for determining human brain tumor malignancy.

Time-dependent room temperature phosphorescent colors from a sulfur-doped carbon dot-based composite for advanced information encryption and anti-counterfeiting applications

Sulfur doping regulates the bandgap of the carbon dots, and time-dependent afterglow color emission is realized in a carbon dot-based composite via the multiple triplet emissions with distinct lifetimes.

Real-time, chirped-pulse heterodyne detection at room temperature with 100 GHz 3-dB-bandwidth mid-infrared quantum-well photodetectors

Thanks to intrinsically short electronic relaxation on the ps time scale, III-V semiconductor unipolar devices are ideal candidates for ultrahigh-speed operation at mid-infrared frequencies. In this work, antenna-coupled, GaAs-based multi-quantum-well photodetectors operating in the 10–11 µm range are demonstrated, with a responsivity of 0.3 A/W and a 3-dB-cutoff bandwidth of 100 GHz at room temperature. The frequency response is measured up to 220 GHz: beyond 100 GHz we find a roll-off dominated by the 2.5-ps-long recombination time of the photo-excited electrons. The potential of the detectors is illustrated by setting up an experiment where the time dependent emission frequency of a quantum cascade laser operated in pulsed mode is measured electronically and in real time, over a frequency range >60GHz. By exploiting broadband electronics, and thanks to its high signal-to-noise ratio, this technique allows the acquisition, in a single-shot, of frequency-calibrated, mid-infrared molecular spectra spanning up to 100 GHz and beyond, which is particularly attractive for fast, active remote sensing applications in fields such as environmental or combustion monitoring.

Accreting black holes skewing and bending the optical emission from massive Wolf–Rayet companions – a case study of IC10 X-1

ABSTRACT We present a statistical analysis of the He ii 4686 emission line in the spectra of the black hole and Wolf–Rayet (WR) star of the high-mass X-ray binary IC10 X-1. This line is visibly skewed, and the third moment (skewness) varies with the binary’s orbital phase. We describe a new method of extracting such weak/faint features lying barely above a noisy continuum. Using the moments of these features, we have been able to decompose these skewed lines into two symmetric Gaussian profiles as a function of the orbital phase. The astrophysical implications of this decomposition are significant due to the complex nature of wind–accretion stream interactions in such binary systems. Previous studies have already shown a 0.25 phase lag in the radial velocity curve of the star and the X-ray eclipse, which indicates that the He ii emitters might be in the stellar wind, hence not tracing the star’s orbital motion. Results from this work further suggest the existence of two separate emitting regions, one in the stellar wind in the shadow of the WR star and another in the accretion stream that impacts the black hole’s outer accretion disc; and the observed skewed He ii lines can be reproduced by superposition of the two corresponding time-dependent Gaussian emission profiles.

Comparison of the time-dependent characteristics between particle mass and particle number emissions during oil heating and emission mitigation strategies

It is important to understand the cooking particles emitted over time to mitigate cooking pollution, but current control strategies fail to consider both particle mass and number emissions. Therefore, this study was designed to compare the differences in time-dependent characteristics of particle mass and number emissions and to propose comprehensive mitigation strategies that consider both characteristics. For this purpose, the effects of various factors on both emissions were analyzed, and time-dependent emission rate models were developed. The time-dependent models obtained were statistically significant (P < 0.001), with most R2 values greater than 0.90. The masses and numbers of particles emitted often varied in the opposite direction. During the smoking stage, corn oil exhibited low particle mass emissions while its particle number emission rate (TERn) reached 109#/s. However, at higher temperatures (T > TDM), the percentage difference in TERn with increasing oil volume decreased from 7.1% to 3.5%, while that in PM2.5 emission rate with decreasing oil volume was almost more than 25%. This indicated that the increased oil volumes were more effective in reducing the particle masses emitted from corn oil than in increasing the numbers of particles emitted, and similar conclusions were also drawn for decreasing oil surface area. Overall, oils exhibiting lower particle mass emissions and lower cooking temperatures were recommended for cooking. Lower oil volumes and larger pans should be used at relatively lower temperatures (T < TDM) primarily to mitigate particle number emissions, while higher oil volumes and smaller pans should be used at higher temperatures to control particle mass emissions.

Noise footprint assessment at a vertiport for different approach and departure procedures of a tilt-wing air-taxi

Community noise at vertiports is one of the most important questions related to upcoming urban air mobility (UAM) operations. While fixed-wing and/or fixed-rotor aircraft can mainly be treated by their changing operational parameters, such as rotor or propeller rpm, tilt-wing or tilt-engine configurations are more difficult to simulate because of their constantly changing noise emission and spatial radiation characteristics. The work presented in this paper is providing an overview of the noise situation at a virtual vertiport which is being approached and departed by a tilt-wing air-taxi in different ways. Several different departure procedures are simulated with the same generic air-taxi. For the noise emission semi-empiric methods were used. During the air-taxi's descent and climb, different tilt configurations are included, mainly defined by the time dependent engine's tilt-angle, but also related to different approach paths. Each approach or departure procedure is generating individually time dependent changing noise emission characteristics which are used for noise footprint mapping around the touch-down or lift-off point. Different noise metrics are computed, including some which are representative to indicate noise annoyance among the vertiport's neighborhood. It is expected that each procedure will generate its own specific community noise situation in the vicinity of the vertiport, and thus may provide an early recommenddation for later operations. The results are compared towards each other. Additionally, a simulated certification flyover according to ICAO Chapter 13 - which is about the noise certification of tilt-rotor aircraft - is set into relation to the vertiport's community noise.

A series of zinc coordination compounds showing persistent luminescence and reversible photochromic properties via charge transfer

Long persistent luminescence materials have wide application prospects in the fields of optical communication, sensors, and anticounterfeiting. Recently, some researchers have proved the feasibility of charge transfer effect in the construction of visible light excited room temperature phosphorescence (RTP) materials. However, materials with electronic effects require elaborate design to exhibit long-lived phosphorescence. Herein, a series of coordination compounds based on viologen ligand HL⋅Cl (4-carboxybenzyl)-4,4′-bipyridinium chloride) and Zn2+ with benzoic acid derivatives (o-, m-, p-phthalic acid) were reported. They exhibit not only reversible photochromic properties, but also long-lived persistent phosphorescence. Three complexes possess different structures through different auxiliary ligands with different optical physical properties. Complex 1 exhibits dynamic phosphorescence emission at low temperatures. Interestingly, we synthesized the first viologen complex (complex 2) with excitation wavelength dependent fluorescence, and the emission color gradually changed from blue to red with the increase of excitation wavelength. In addition, the applications of three complexes in data encryption and anticounterfeiting are further demonstrated. This work not only presents coordination compounds with dynamic afterglow materials, excitation wavelength- and time-dependent emission properties, but also provides a new strategy for the charge transfer effect in visible light-excited RTP materials.

Factors influencing ambient particulate matter in Delhi, India: Insights from machine learning

Concentrations of ambient particulate matter (PM) depend on various factors including emissions of primary pollutants, meteorology and chemical transformations. New Delhi, India is the most polluted megacity in the world and routinely experiences extreme pollution episodes. As part of the Delhi Aerosol Supersite study, we measured online continuous PM1 (particulate matter of size less than 1 μm) concentrations and composition for over five years starting January 2017, using an Aerosol Chemical Speciation Monitor (ACSM). Here, we describe the development and application of machine learning models using random forest regression to estimate the concentrations, composition, sources and dynamics of PM in Delhi. These models estimate PM1 species concentrations based on meteorological parameters including ambient temperature, relative humidity, planetary boundary layer height, wind speed, wind direction, precipitation, agricultural burning fire counts, solar radiation and cloud cover. We used hour of day, day of week and month of year as proxies for time-dependent emissions (e.g., emissions from traffic during rush hours). We demonstrate the applicability of these models to capture temporal variability of the PM1 species, to understand the influence of individual factors via sensitivity analyses, and to separate impacts of the COVID-19 lockdowns and associated activity restrictions from impacts of other factors. Our models provide new insights into the factors influencing ambient PM1 in New Delhi, India, demonstrating the power of machine learning models in atmospheric science applications.Copyright © 2023 American Association for Aerosol Research

Tuning Emission Lifetimes of Ir(C^N)2(acac) Complexes with Oligo(phenyleneethynylene) Groups

Emissive compounds with long emission lifetimes (μs to ms) in the visible region are of interest for a range of applications, from oxygen sensing to cellular imaging. The emission behavior of Ir(ppy)2(acac) complexes (where ppy is the 2-phenylpyridyl chelate and acac is the acetylacetonate chelate) with an oligo(para-phenyleneethynylene) (OPE3) motif containing three para-rings and two ethynyl bridges attached to acac or ppy is examined here due to the accessibility of the long-lived OPE3 triplet states. Nine Ir(ppy)2(acac) complexes with OPE3 units are synthesized where the OPE3 motif is at the acac moiety (aOPE3), incorporated in the ppy chelate (pOPE3) or attached to ppy via a durylene link (dOPE3). The aOPE3 and dOPE3 complexes contain OPE3 units that are decoupled from the Ir(ppy)2(acac) core by adopting perpendicular ring-ring orientations, whereas the pOPE3 complexes have OPE3 integrated into the ppy ligand to maximize electronic coupling with the Ir(ppy)2(acac) core. While the conjugated pOPE3 complexes show emission lifetimes of 0.69-32.8 μs similar to the lifetimes of 1.00-23.1 μs for the non-OPE3 Ir(ppy)2(acac) complexes synthesized here, the decoupled aOPE3 and dOPE3 complexes reveal long emission lifetimes of 50-625 μs. The long lifetimes found in aOPE3 and dOPE3 complexes are due to intramolecular reversible electronic energy transfer (REET) where the long-lived triplet-state metal to ligand charge transfer (3MLCT) states exchange via REET with the even longer-lived triplet-state localized OPE3 states. The proposed REET process is supported by changes observed in excitation wavelength-dependent and time-dependent emission spectra from aOPE3 and dOPE3 complexes, whereas emission spectra from pOPE3 complexes remain independent of the excitation wavelength and time due to the well-established 3MLCT states of many Ir(ppy)2(acac) complexes. The long lifetimes, visible emission maxima (524-526 nm), and photoluminescent quantum yields of 0.44-0.60 for the dOPE3 complexes indicate the possibility of utilizing such compounds in oxygen-sensing and cellular imaging applications.

Efficient stabilization of cyanonaphthalene by fast radiative cooling and implications for the resilience of small PAHs in interstellar clouds

After decades of searching, astronomers have recently identified specific Polycyclic Aromatic Hydrocarbons (PAHs) in space. Remarkably, the observed abundance of cyanonaphthalene (CNN, C10H7CN) in the Taurus Molecular Cloud (TMC-1) is six orders of magnitude higher than expected from astrophysical modeling. Here, we report unimolecular dissociation and radiative cooling rate coefficients of the 1-CNN isomer in its cationic form. These results are based on measurements of the time-dependent neutral product emission rate and kinetic energy release distributions produced from an ensemble of internally excited 1-CNN+ studied in an environment similar to that in interstellar clouds. We find that Recurrent Fluorescence – radiative relaxation via thermally populated electronic excited states – efficiently stabilizes 1-CNN+, owing to a large enhancement of the electronic transition probability by vibronic coupling. Our results help explain the anomalous abundance of CNN in TMC-1 and challenge the widely accepted picture of rapid destruction of small PAHs in space.

Time Resolved Raman Scattering of Molecules: A Quantum Mechanics Approach with Stochastic Schroedinger Equation.

Raman scattering is a very powerful tool employed to characterize molecular systems. Here we propose a novel theoretical strategy to calculate the Raman cross-section in time domain, by computing the cumulative Raman signal emitted during the molecular evolution in time. Our model is based on a numerical propagation of the vibronic wave function under the effect of a light pulse of arbitrary shape. This approach can therefore tackle a variety of experimental setups. Both resonance and nonresonance Raman scattering can be retrieved, and also the time-dependent fluorescence emission is computed. The model has been applied to porphyrin considering both resonance and nonresonance conditions and varying the incident field duration. Moreover the effect of the vibrational relaxation, which should be taken into account when its time scale is similar to that of the Raman emission, has been included through the stochastic Schroedinger equation approach.

Near-infrared emission in Ho3+-doped Yb3Ga5O12 garnet nanocrystals

The single-phase Ho3+-doped Yb3Ga5O12 garnet nanocrystals were synthesized by the sol-gel combustion technique using citric acid. Their structure, morphology and chemical composition were examined by the powder X-ray diffraction, attenuated total reflectance-Fourier transform infrared spectroscopy and Energy-dispersive X-ray spectrometry with the scanning electron microscope. The observed strong absorption band associated with the high content of Yb3+ ensures efficient excitation of the Yb15−xHoxGa25O60 garnets using 980 nm radiation. The near-infrared emission originating from the Ho3+: 5I6 → 5I8 and 5I7 → 5I8 transitions is studied using the measurement of the steady-state and time-dependent emission spectra. The proposed luminescence mechanism is discussed based on the Yb3+ → Ho3+ energy transfer with contribution of the Ho3+ → Yb3+ energy back transfer and Ho3+ ↔ Ho3+ cross-relaxation processes.

Spectroscopic characterization of rare events in colloidal particle stochastic thermodynamics.

Given the remarkable developments in synthetic control over chemical and physical properties of colloidal particles, it is interesting to see how stochastic thermodynamics studies may be performed with new, surrogate, or hybrid model systems. In the present work, we apply stochastic dynamics and nonlinear optical light-matter interaction simulations to study nonequilibrium trajectories of individual Yb (III):Er (III) colloidal particles driven by two-dimensional dynamic optical traps. In addition, we characterize the role of fluctuations at the single-particle level by analyzing position trajectories and time-dependent upconversion emission intensities. By integrating these two complementary perspectives, we show how the methods developed here can be used to characterize rare events.