Thermodynamic Equilibrium Conditions Research Articles

First Extragalactic Detection of Thermal Hydroxyl (OH) 18 cm Emission in M31 Reveals Abundant CO-faint Molecular Gas

The most abundant interstellar molecule, molecular hydrogen (H2), is practically invisible in cold molecular clouds. Astronomers typically use carbon monoxide (CO) to trace the bulk distribution and mass of H2 in our galaxy and many others. CO observations alone fail to trace a significant component of molecular gas known as “CO-dark” molecular gas, which can be probed with molecules such as OH and CH. We present an extremely sensitive pilot search for the 18 cm hydroxyl (OH) lines in the Andromeda galaxy (M31) with the 100 m Robert C. Byrd Green Bank Telescope. We successfully detected the 1665 and 1667 MHz OH lines in faint emission. The 1665/1667 MHz line ratio displays the characteristic 5:9 ratio predicted under conditions of local thermodynamic equilibrium. To our knowledge, this is the first detection of nonmaser 18 cm OH emission in another galaxy. We compare our OH and H i observations with archival CO (1–0) observations. Our OH detection position overlaps with the previously discovered Arp Outer Arm in CO. Our best estimates show that the amount of H2 traced by OH is 100%–140% higher than the amount traced by CO in this sight line. The amount of dark molecular gas implied by dust data supports this conclusion. We conclude that the 18 cm OH lines hold promise as a valuable tool for mapping of the “CO-dark” and “CO-faint” molecular gas phase in nearby galaxies, especially with upcoming multibeam, phased-array feed receivers on radio telescopes, which will allow for drastically improved mapping speeds of faint signals.

An improved and extended parameterization of the CO2 15 µm cooling in the middle and upper atmosphere (CO2_cool_fort-1.0)

Abstract. The radiative infrared cooling of CO2 in the middle atmosphere, where it emits under non-local thermodynamic equilibrium (non-LTE) conditions, is a crucial contribution to the energy balance of this region and hence to establishing its thermal structure. The non-LTE computation is too CPU time-consuming to be fully incorporated into climate models, and hence it is parameterized. The most used parameterization of the CO2 15 µm cooling for Earth's middle and upper atmosphere was developed by Fomichev et al. (1998). The valid range of this parameterization with respect to CO2 volume mixing ratios (VMRs) is, however, exceeded by the CO2 of several scenarios considered in the Coupled Climate Model Intercomparison Projects, in particular the abrupt-4×CO2 experiment. Therefore, an extension, as well as an update, of that parameterization is both needed and timely. In this work, we present an update of that parameterization that now covers CO2 volume mixing ratios in the lower atmosphere from ∼0.5 to over 10 times the CO2 pre-industrial value of 284 ppmv (i.e. 150 to 3000 ppmv). Furthermore, it is improved by using a more contemporary CO2 line list and the collisional rates that affect the CO2 cooling rates. Overall, its accuracy is improved when tested for the reference temperature profiles as well as for measured temperature fields covering all expected conditions (latitude and season) of the middle atmosphere. The errors obtained for the reference temperature profiles are below 0.5 K d−1 for the present-day and lower CO2 VMRs. Those errors increase to ∼1–2K d−1 at altitudes between 110 and 120 km for CO2 concentrations of 2 to 3 times the pre-industrial values. For very high CO2 concentrations (4 to 10 times the pre-industrial abundances), those errors are below ∼1 K d−1 for most regions and conditions, except at 107–135 km, where the parameterization overestimates them by ∼1.2 %. These errors are comparable to the deviation of the non-LTE cooling rates with respect to LTE at about 70 km and below, but they are negligible (several times smaller) above that altitude. When applied to a large dataset of global (pole to pole and four seasons) temperature profiles measured by MIPAS (Michelson Interferometer for Passive Atmospheric Spectroscopy) (middle- and upper-atmosphere mode), the errors of the parameterization for the mean cooling rate (bias) are generally below 0.5 K d−1, except between 5×10-3 and 3×10-4 hPa (∼85–98 km), where they can reach biases of 1–2 K d−1. For single-temperature profiles, the cooling rate error (estimated by the root mean square – rms – of a statistically significant sample) is about 1–2 K d−1 below 5×10-3 hPa (∼85 km) and above 2×10-4 hPa (∼102 km). In the intermediate region, however, it is between 2 and 7 K d−1. For elevated stratopause events, the parameterization underestimates the mean cooling rates by 3–7 K d−1 (∼10 %) at altitudes of 85–95 km and the individual cooling rates show a significant rms (5–15 K d−1). Further, we have also tested the parameterization for the temperature obtained by a high-resolution version of the Whole Atmosphere Community Climate Model (WACCM-X), which shows a large temperature variability and wave structure in the middle atmosphere. In this case, the mean (bias) error of the parameterization is very small, smaller than 0.5 K d−1 for most atmospheric layers, reaching only maximum values of 2 K d−1 near 5×10-4 hPa (∼ 96 km). The rms has values of 1–2 K d−1 (∼20 %) below ∼2×10-2 hPa (∼80 km) and values smaller than 4 K d−1 (∼2 %) above 10−4 hPa (∼105 km). In the intermediate region between ∼5×10-3 and ∼2×10-4 hPa (85–102 km), the rms is in the range of 5–12 K d−1. While these values are significant in percentage at ∼5×10-3–5×10-4 hPa, they are very small above ∼5×10-4 hPa (96 km). The routine is very fast, taking (1.5–7.5) ×10-5 s, depending on the extension of the atmospheric profile, the processor and the Fortran compiler.

A collision operator for describing dissipation in noncanonical phase space

The phase space of a noncanonical Hamiltonian system is partially inaccessible due to dynamical constraints (Casimir invariants) arising from the kernel of the Poisson tensor. When an ensemble of noncanonical Hamiltonian systems is allowed to interact, dissipative processes eventually break the phase space constraints, resulting in a thermodynamic equilibrium described by a Maxwell–Boltzmann distribution. However, the time scale required to reach Maxwell–Boltzmann statistics is often much longer than the time scale over which a given system achieves a state of thermal equilibrium. Examples include diffusion in rigid mechanical systems, as well as collisionless relaxation in magnetized plasmas and stellar systems, where the interval between binary Coulomb or gravitational collisions can be longer than the time scale over which stable structures are self-organized. Here, we focus on self-organizing phenomena over spacetime scales such that particle interactions respect the noncanonical Hamiltonian structure, but yet act to create a state of thermodynamic equilibrium. We derive a collision operator for general noncanonical Hamiltonian systems, applicable to fast, localized interactions. This collision operator depends on the interaction exchanged by colliding particles and on the Poisson tensor encoding the noncanonical phase space structure, is consistent with entropy growth and conservation of particle number and energy, preserves the interior Casimir invariants, reduces to the Landau collision operator in the limit of grazing binary Coulomb collisions in canonical phase space, and exhibits a metriplectic structure. We further show how thermodynamic equilibria depart from Maxwell–Boltzmann statistics due to the noncanonical phase space structure, and how self-organization and collisionless relaxation in magnetized plasmas and stellar systems can be described through the derived collision operator.

Multidimensional Electrochemistry Decodes the Operando Mechanism of Hydrogen Oxidation

AbstractBeing an efficient approach to the utilization of hydrogen energy, the hydrogen oxidation reaction (HOR) is of particular significance in the current carbon‐neutrality time. Yet the mechanistic picture of the HOR is still blurred, mostly because the elemental steps of this reaction are rapid and highly entangled, especially when deviating from the thermodynamic equilibrium state. Here we report a strategy for decoding the HOR mechanism under operando conditions. In addition to the wide‐potential‐range I–V curves obtained using gas diffusion electrodes, we have applied the AC impedance spectroscopy to provide independent and complementary kinetic information. Combining multidimensional data sources has enabled us to fit, in mathematical rigor, the core kinetic parameter set in a 5‐D data space. The reaction rate of the three elemental steps (Tafel, Heyrovsky, and Volmer reactions), as a function of the overpotential, can thus be distilled individually. Such an undocumented kinetic picture unravels, in detail, how the HOR is controlled by the elemental steps on polarization. For instance, at low polarization region, the Heyrovsky reaction is relatively slow and can be ignored; but at high polarization region, the Heyrovsky reaction will surpass the Tafel reaction. Additionally, the Volmer reaction has been the fastest within overpotentials of interest. Our findings not only offer a better understanding of the HOR mechanism, but also lay the foundation for the development of improved hydrogen energy utilization systems.

Multidimensional Electrochemistry Decodes the Operando Mechanism of Hydrogen Oxidation.

Being an efficient approach to the utilization of hydrogen energy, the hydrogen oxidation reaction (HOR) is of particular significance in the current carbon-neutrality time. Yet the mechanistic picture of the HOR is still blurred, mostly because the elemental steps of this reaction are rapid and highly entangled, especially when deviating from the thermodynamic equilibrium state. Here we report a strategy for decoding the HOR mechanism under operando conditions. In addition to the wide-potential-range I-V curves obtained using gas diffusion electrodes, we have applied the AC impedance spectroscopy to provide independent and complementary kinetic information. Combining multidimensional data sources has enabled us to fit, in mathematical rigor, the core kinetic parameter set in a 5-D data space. The reaction rate of the three elemental steps (Tafel, Heyrovsky, and Volmer reactions), as a function of the overpotential, can thus be distilled individually. Such an undocumented kinetic picture unravels, in detail, how the HOR is controlled by the elemental steps on polarization. For instance, at low polarization region, the Heyrovsky reaction is relatively slow and can be ignored; but at high polarization region, the Heyrovsky reaction will surpass the Tafel reaction. Additionally, the Volmer reaction has been the fastest within overpotentials of interest. Our findings not only offer a better understanding of the HOR mechanism, but also lay the foundation for the development of improved hydrogen energy utilization systems.

EMISSA: Exploring millimetre indicators of solar-stellar activity III. Comparison of Ca II indices and millimetre continua in a 3D model atmosphere

Amongst several spectral lines, some of the strongest chromospheric diagnostics are offered by the Ca II H K lines. These lines can be used to gauge the temperature stratification of the atmosphere since the line core and wings are formed in different regions of the solar atmosphere. Furthermore, the Ca II lines act as tracers for the magnetic structure of the solar atmosphere, as the line cores are formed in the upper chromosphere even though they are formed in non-local thermodynamic equilibrium (NLTE). In contrast, the formation of millimetre (mm) continuum radiation occurs under local thermodynamic equilibrium (LTE) conditions. As a result, the brightness temperatures obtained from observations with the Atacama Large Millimetre/Submillimetre Array (ALMA) offer a complementary perspective on the activity and thermal structure of stellar atmospheres. The overall aim is to establish more robust solar/stellar activity indicators using ALMA observations in comparison with classical diagnostics, such as the s index and infrared triplet (IRT) index. We employed the 1.5D radiative transfer codes RH1.5D and advanced radiative transfer (ART) to compute the synthetic spectra for the Ca II lines and the millimetre (mm) continua, respectively. These calculations were performed using an enhanced network atmosphere model, which incorporates non-equilibrium hydrogen ionisation generated by the state-of-the-art 3D radiation magnetohydrodynamics (rMHD) Bifrost code. To account for the limited spatial resolution of ALMA, we simulated the effect using a Gaussian point spread function (PSF). Additionally, we analysed the correlations and slopes of scatter plots between the Ca II indices and mm continuum for the original and degraded resolutions, focusing on the entire simulation box, quiet Sun regions, and enhanced network patches separately. The activity indices generated from these lines could further be used to compare the spectra of Sun-like stars with the solar spectrum. We present a comparative study between synthetic continuum brightness temperature maps at mm wavelengths (0.3 mm to 8.5 mm) and the Ca II activity indices; namely, the s index and infrared triplet (IRT) index. The Ca II activity indices and mm brightness temperatures are weakly correlated at the high resolution, with the highest correlation observed at a wavelength of 0.3 mm, corresponding to ALMA band 10. As the resolution decreases, the correlation consistently increases. Conversely, the slopes exhibit a decreasing trend with increasing wavelength, while the degradation of resolution does not noticeably affect the calculated slopes. As the spatial resolution decreases, the standard deviations of the Ca II activity indices and brightness temperatures decrease, while the correlations between them increase. However, the slopes do not exhibit significant changes. Consequently, these relationships could be valuable for calibrating the mm continuum maps obtained through ALMA observations.

АНАЛІЗ РОЗВИТКУ РЕАКЦІЇ ОКИСЛЕННЯ ВУГЛЕЦЮ НИЗЬКОВУГЛЕЦЕВОЇ СТАЛІ В КОВШІ ПІД ВАКУУМОМ

The object of research is the process of vacuuming steel in a ladle. The purpose of the study is to determine the degree of approach of degassing reactions to equilibrium and removal rates by articles. Research methods - theoretical studies are based on the basic provisions of physical chemistry and the theory of metallurgical processes, thermodynamic calculations of the non-equilibrium reactions of degassing. Scientific novelty - in vacuum degassing processes, the approximation of the corresponding reactions to equilibrium plays a significant role, in industrial vacuum installations, the equilibrium between carbon and oxygen dissolved in steel is not achieved due to ex-tremely small concentrations of interacting substances, the speed of the chemical reaction decreases so much that it does not allow for processing time to even approach the state of thermodynamic equilibrium. Practical significance - to ensure a high degree of implementation of the deoxidizing ability of carbon in vacuum conditions, it is neces-sary to: apply the main lining of steel pouring ladles; maintain a high basicity of slag and a minimum content of iron oxides in it; mix the melt in the ladle with an inert gas to facilitate the conditions for the nucleation of carbon oxidation reaction products.

Modeling of vacuuming of low-carbon steel in a ladle taking into account the approach of degasation reactions to equilibrium

The object of research is the process of vacuuming steel in a ladle. The purpose of the study is to determine the degree of approach of degassing reactions to equilibrium and removal rates by articles. Research methods - theoretical studies are based on the basic provisions of physical chemistry and the theory of metallurgical processes, thermodynamic calculations of the non-equilibrium reactions of degassing. Scientific novelty - in vacuum degassing processes, the approximation of the corresponding reactions to equilibrium plays a significant role, in industrial vacuum installations, the equilibrium between carbon and oxygen dissolved in steel is not achieved due to extremely small concentrations of interacting substances, the speed of the chemical reaction decreases so much that it does not allow for processing time to even approach the state of thermodynamic equilibrium. Practical significance - to ensure a high degree of implementation of the deoxidizing ability of carbon in vacuum conditions, it is necessary to: apply the main lining of steel pouring ladles; maintain a high basicity of slag and a minimum content of iron oxides in it; mix the melt in the ladle with an inert gas to facilitate the conditions for the nucleation of carbon oxidation reaction products.

On the stability of a particular class of one-dimensional states of dynamic equilibrium of the Vlasov–Poisson electron gas

The one-dimensional problem of the linear stability of dynamic states of local thermodynamic equilibria with respect to small perturbations was studied for the case when the Vlasov–Poisson electron gas contains electrons with a stationary distribution function that is constant in physical space and variable in a continuum of velocities. The absolute instability of all considered one-dimensional dynamic states of any local thermodynamic equilibrium was proved using the direct Lyapunov method. The scope of applicability of the Newcomb–Gardner–Rosenbluth sufficient condition for linear stability was outlined. An a priori exponential estimation was obtained for the rise of small one-dimensional perturbations from below. Analytic counterexamples to the spectral Newсomb–Gardner theorem and the Penrose criterion were constructed. Earnshaw’s theorem was extended from classical mechanics tostatistical one.

Effect of Femtosecond Ultraviolet and Infrared Laser Wavelength on Plasma Characteristics of Metals, Ceramics and Glass Samples Using Femtosecond Laser-Induced Breakdown Spectroscopy.

In this work, we present studies on the effect of laser wavelengths on the laser-induced plasma characterization using a femtosecond (fs) ytterbium-doped potassium-gadolinium tungstate (Yb:KGW) laser. Plasma plumes of copper, steel, ceramics, and glass samples were induced using a multiple shot of 200 fs laser pulses with 1030 nm and 343 nm wavelengths at fixed laser fluence () and analyzed using the laser-induced breakdown spectroscopy (LIBS) technique. Time-resolved fs-LIBS measurements were performed on the same set of samples and under the same experimental conditions. For the calculation of plasma parameters, the set of spectral lines of Cu(I) (for copper sample), Fe(I) (for steel sample), and Ca(I), K(I) (for glass and ceramics samples) were observed. The plasma electron temperature and density were evaluated from the Boltzmann plots and Stark-broadening profiles of the plasma spectral lines, assuming the local thermodynamic equilibrium condition. Time-resolved plasma temperature and electron density for fs-LIBS using ultraviolet (UV) and infrared (IR) laser wavelengths were analyzed and no significant dependence on fs laser wavelength was observed for any of the samples. However, for all samples the signal-to-noise ratio (SNR) significantly increased using UV laser radiation: copper (), steel (), glass (), and ceramics (). Therefore, by using a fs UV laser wavelength for laser-induced breakdown spectroscopy experiments, for certain materials the SNR and at the same time the limit of detection can be significantly enhanced.

Thermodynamic Equilibrium State Prediction by Deep Learning Method

Thermodynamic Equilibrium State Prediction by Deep Learning Method

On thermodynamic stability of black holes. Part I: classical stability

We revisit the classical thermodynamic stability of the standard black hole solutions by implementing the intrinsic necessary and sufficient conditions for stable global and local thermodynamic equilibrium. The criteria for such equilibria are quite generic and well-established in classical thermodynamics, but they have not been fully utilized in black hole physics. We show how weaker or incomplete conditions could lead to misleading or incorrect results for the thermodynamic stability of the system. We also stress the importance of finding all possible local heat capacities in order to fully describe the classical equilibrium picture of black holes. Finally, we thoroughly investigate the critical and phase transition curves and the limits of the classical analysis. This paper is the first in the line of intended works on thermodynamic stability of black holes in modified theories of gravity and holography.

Thermodynamic equilibrium state calculations for oxidation and corrosion reactions of B4C and oxide-based neutron absorber compounds in reactor control rods

The challenges associated with conventional boron carbide (B4C) control rod materials, including helium gas accumulation and susceptibility to oxidation and corrosion in various environments, have been thoroughly explored. To address these issues, a comprehensive investigation into the potential of oxide-based neutron absorber compounds for control rods has been undertaken. Thermodynamic equilibrium state calculations have been conducted to assess the oxidation and corrosion reactions of various neutron absorber materials (Gd, Hf, Sm, Er, Eu, Dy-based oxide), including B4C, in various environments such as oxygen, steam, air, and air–steam mixtures. The results have unveiled vulnerabilities of B4C in these environments, notably the generation of gases such as H2, CO, and boron compounds. Furthermore, neutron absorber oxide materials have exhibited potential susceptibility to oxidation and corrosion in steam environments. Consequently, the potential of oxide-based neutron absorber compounds, formed by combining neutron absorber oxide materials with highly oxidation-resistant substances (ZrO2, TiO2), has been explored. Thermodynamic equilibrium state calculations indicate that these compounds maintain robust resistance to oxidation and corrosion across various environments. This paper demonstrates the superiority of oxide-based neutron absorber compounds as alternatives to existing boron carbide neutron absorber materials. Additionally, the oxide-based neutron absorber compounds are expected to extend the lifetime of the LWR control rod as well as improve stability and resistance to oxidation and corrosion.

Measurement of medium-voltage AC air arc temperature and particle number density based on dual-wavelength Moiré deflection technology

AC air arcs are generated in medium-voltage (MV) power systems under the effect of harsh weather conditions, equipment aging, and high penetration of distributed generation, threatening equipment and public safety. The arc current and temperature are low due to the wide application of arc suppression devices. In this scenario, the MV AC air arc does not satisfy the local thermodynamic equilibrium (LTE) condition. In addition, the repeated arcing and extinguishing processes further complicate the arc discharge mechanism, which bring challenges in the modeling and detection of MV AC air arcs. Experimental methods are a direct and efficient approach to determine the properties of arc plasmas. In this study, a dual-wavelength Moiré deflection diagnostic system was established to determine the time evolution of the particle density and radial distribution of the temperature in an MV AC air arc without relying on the LTE assumption. The electron number density and heavy particle number density change transiently during the arc discharge process and change gradient along the radial direction. The heavy particle temperature and electron temperature were then calculated based on the measured particle number density. During the arcing stage, the temperature of the electrons exceeded that of the heavy particles significantly, and the arc deviated from LTE. Finally, the limitations of the traditional single-wavelength Moiré deflection method are analyzed. The classic single-wavelength Moiré deflection method, while capable of estimating heavy particle temperature in plasma, exhibits a significant error in electron density estimation compared to the dual-wavelength Moiré deflection method.

Thermo-Mechanical analysis of laminated Doubly-Curved Shells: Higher order Equivalent Layer-Wise formulation

The paper presents a refined two-dimensional formulation for the thermo-mechanical analysis of laminated doubly-curved shell structures under thermodynamic equilibrium conditions. Both the kinematic configuration variables and the temperature variation with respect to the natural equilibrium state are described with a generalized formulation, following the Equivalent Layer-Wise (ELW) approach employing higher order polynomials, along with some proper zigzag functions. The governing equations are derived from the stationary configuration of the Helmholtz free energy of the system, and a semi-analytical solution is found. In the post-processing phase, the Fourier-based Generalized Differential Quadrature (F-GDQ) is applied to recover the actual three-dimensional response of the doubly-curved shell solid, and very accurate results are obtained for the quantities of both mechanical and heat conduction problems. In addition, the integrals occurring in the theory are performed numerically with the Taylor-based Generalized Integral Quadrature (GTIQ), showing a high level of accuracy with a reduced number of sample points. The model is validated in some case studies, where the accuracy of the model is shown, and the numerical predictions are successfully compared with those ones from refined three-dimensional numerical simulations. After that, an extensive set of parametric investigations is reported, pointing out the effects of the panel curvature, lamination schemes and different levels of coupling on the thermo-mechanical structural behavior of the investigated panels.

Collisional excitation of propyne (CH3CCH) by He atoms

Context. A detailed interpretation of the detected emission lines of environments where propyne (or methyl acetylene, CH3CCH) is observed requires access to its collisional rate coefficients with the most abundant species in the interstellar medium, namely, helium (He) or molecular hydrogen (H2). Aims. We present the first three-dimensional potential energy surface (3D PES) for the CH3CCH-He molecular complex. We study the dynamics of the collision and report the first set of rate coefficients for temperatures up to 100 K for the collisional excitation of the lowest 60 ortho rotational levels and 60 para rotational levels of CH3CCH by He atoms. Methods. We computed the 3D PES with the explicitly correlated coupled-cluster with a single-, double-, and perturbative triple-excitation method in conjunction with the augmented correlation-consistent triple zeta basis set (CCSD(T)-F12a/aug-cc-pVTZ). The 3D PES was then fitted to an analytical function and scattering computations of pure rotational (de-)excitation of CH3CCH by collision with He atoms were performed. State-to-state cross-sections were computed using the close coupling method for total energies up to 100 cm−1 and with the coupled states approximation at higher energies for both the ortho- and para- symmetries of CH3CCH. Results. The PES we obtained is characterised by a large anisotropy and a potential well depth of 51.04 cm−1. By thermally averaging the collisional cross-sections, we determined the quenching rate coefficients for kinetic temperatures up to 100 K. A strong and even Δj propensity rule at almost all collision energies is present for CH3CCH-He complex. To evaluate the impact of rate coefficients on the analysis of observations, we carried out non-local thermodynamic equilibrium radiative transfer computations of the excitation temperatures and we demonstrate that local thermodynamic equilibrium conditions are not typically fulfilled for the propyne molecule.

A Mode-Coupling Model of Colloid Thermophoresis in Aqueous Systems: Temperature and Size Dependencies of the Soret Coefficient.

Thermophoresis allows for the manipulation of colloids in systems containing a temperature gradient. A deep understanding of the phenomena at the molecular level allows for increased control and manipulation strategies. We developed a microscopic model revealing different coupling mechanisms for colloid thermophoresis under local thermodynamic equilibrium conditions. The model has been verified through comparison with a variety of previously published experimental data and shows good agreement across significantly different systems. We found five different temperature-dependent contributions to the Soret coefficient, two from bulk properties and three from interfacial interactions between the fluid medium and the colloid. Our analysis shows that the Soret coefficient for nanosized particles is governed by the competition between the electrostatic and hydration interfacial interactions, while bulk contributions become more pronounced for protein systems. This theory can be used as a guide to design thermophoretic transport, which is relevant for sensing, focusing, and separation at the microscale.

Modulation of Heterotypic and Homotypic Interactions to Visualize the Evolution of Organic Aggregates in a Fluorescence Turn-on Manner.

The abnormal evolution of membrane-less organelles into amyloid fibrils is a causative factor in many neurodegenerative diseases. Fundamental research on evolving organic aggregates is thus instructive for understanding the root causes of these diseases. In-situ monitoring of evolving molecular aggregates with built-in fluorescence properties is a reliable approach to reflect their subtle structural variation. To increase the sensitivity of real-time monitoring, we presented organic aggregates assembled by TPAN-2MeO, which is a triphenyl acrylonitrile derivative. TPAN-2MeO showed a morphological evolution with distinct turn-on emission. Upon rapid nanoaggregation, it formed non-emissive spherical aggregates in the kinetically metastable state. Experimental and simulation results revealed that the weak homotypic interactions between the TPAN-2MeO molecules liberated their molecular motion for efficient non-radiative decay, and the strong heterotypic interactions between TPAN-2MeO and water stabilized the molecular geometry favorable for the non-fluorescent state. After ultrasonication, the decreased heterotypic interactions and increased homotypic interactions acted synergistically to allow access to the emissive thermodynamic equilibrium state with a decent photoluminescence quantum yield (PLQY). The spherical aggregates were eventually transformed into micrometer-sized blocklike particles. Under mechanical stirring, the co-assembly of TPAN-2MeO and Pluronic F-127 formed uniform fluorescent platelets, inducing a significant enhancement in PLQY. These results decipher the stimuli-triggered structural variation of organic aggregates with concurrent sensitive fluorescence response and pave the way for a deep understanding of the evolutionary events of biogenic aggregates.

Comparison of excitation temperature of a laser-produced plasma by combining emission and absorption spectroscopy

Measurement of the temporal evolution of laser-produced plasma temperature is very important for many of its applications, and several plasma diagnostic tools are routinely used by researchers. However, it is very challenging to measure the properties of the plasma at the early and late times of its evolution using a single diagnostic tool. In this study, we combined emission and laser absorption spectroscopy to compare the excitation temperatures of a laser-produced uranium plasma system. Several U I transitions in the near-infrared spectral range (775–800 nm) were considered, and the Boltzmann plot method was used to measure the excitation temperatures using both emission and absorption spectroscopy. Emission spectroscopy provided early-time temperature measurements of the plasma up to times 2–20 µs, while absorption spectroscopy provided temperature measurements at late times of plasma evolution (for times 5–80 µs). The emission and absorbance of U I transitions were found to follow the Boltzmann distribution, indicating the plasma is likely in the state of local thermodynamic equilibrium even at late times of its lifetime. The emission and absorption-based time-resolved excitation temperatures demonstrated good agreement at earlier times (≤15 µs) in the overlapped temporal region, while a deviation in the measured values was seen at times (≥15 µs), and potential reasons for such a disagreement are discussed.

Comparing the impact of different adsorbed layers on the local glass transition of polymer matrices.

Chain adsorption to nanofiller interfaces creating bound layers has become central to understanding property changes in polymer nanocomposites. We determine the impact different kinds of adsorbed layers can have on the local glass transition temperature Tg of polymer matrices in a model film system using a localized fluorescence method. This work compares the adsorption and desorption of adsorbed layers grown in solution with the solution washing characteristics of adsorbed layers formed in the melt, leveraging knowledge about polymer adsorption in solution to infer the structure of adsorbed layers formed in the melt. In the limit of zero concentration after a long time in solution, we find that both kinds of adsorbed layers reach the same limiting adsorbed amount h∞(c → 0) ≈ 1 nm, appearing to evolve to the same thermodynamic equilibrium state of a near monolayer of surface coverage. We propose that melt annealing leads to a coarsening of polymer segment-surface contacts, increasing the length of trains and shrinking loops and tails, slowing the subsequent kinetics of these adsorbed chains in solution. Considering how the pyrene-labeled chains intermix with the adsorbed layer enables us to discriminate between the impact of tails, loops, and trains as threading of loops takes longer. We find that large fluffy loops, tails, and trains have little to no impact on the local Tg. A large 30K increase in local Tg is observed for 30-minsolvent washed well-annealed films at long intermixing times that we attribute to the threading of small tight loops.