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The power of an optically pumped CH3F laser operating on the 496-micron line has been doubled with the addition of SF6 without any corresponding increase in pump absorption. It is suggested that a near-resonant energy transfer between CH3F and SF6 followed by SF6 deactivation is the mechanism responsible for the enhancement.
The laser-excited fluorescence method has been employed to determine the rate constants for vibrational relaxation of the O3 (010), O3 (100) and O3 (001) levels at 298 K. The fluorescence observations from the O3 (010) level provide direct measurements of the rate for intermode vibrational energy transfer from the coupled nu sub 1 and nu sub 3 modes to the nu sub 2 mode. The slowness of this process indicates the likelihood that the nu sub 1 and/or nu sub 3 modes (rather than the nu sub 2 mode) play a predominant role in the laser-enhanced reaction between vibrationally excited O3 and NO at 298 K.
Achieving multimodal luminescence within a single phosphor is vital for multifunctional applications but remains challenging due to complex color tuning and trap engineering. In this study, we report Pr 3+ and Gd 3+ co‐doped LaAlO 3 (LAO:PG) phosphors, designed through careful modulation of multilevel traps and Pr 3+ → Gd 3+ energy transfer dynamics. These materials exhibit diverse luminescence modes, including down‐conversion luminescence (DCL), up‐conversion luminescence (UCL), persistent luminescence (PersL), optically stimulated luminescence (OSL), and thermally stimulated luminescence (TSL) across a wide spectral range. Unlike previously studied Pr 3+ ‐doped LAO, the co‐doped LAO:PG shows DCL in both UV‐visible and NIR regions and displays ultraviolet‐C UCL under visible excitation. Notably, we observe, for the first time, PersL lasting several minutes in these phosphors—an improvement over the non‐PersL behavior of Pr 3+ ‐only doped LAO. Additionally, the LAO:PG phosphors exhibit strong OSL response. TSL analysis reveals five distinct trap levels linked to these properties. Density functional theory calculations further correlate intrinsic defects to these traps, supporting a proposed mechanism for the observed multimodal luminescence. These findings highlight LAO:PG as a promising platform for developing advanced phosphors with integrated luminescence modes, paving the way for future applications in data storage, phototherapy, and anti‐counterfeiting technologies.
Recent work in the aerothermodynamics community has focused on the development of reduced-order models for thermo-chemical non-equilibrium which avoid the restrictive assumptions of multi-temperature models and the prohibitive cost associated with State-to-State (StS) models. In the present work, this is accomplished by lumping energy states together and assuming groups of states are roughly in equilibrium. As a result, the non-equilibrium behavior of a gas can be captured at a reduced computational cost from a full StS simulation. In this work, we present a hybrid grouping model for studying energy transfer and dissociation in a mixture of nitrogen molecules due to N2-N2 reactions. This is accomplished by making use of a grouping strategy informed by data from the N2-N StS kinetic data. However, due to the massive computational cost associated with constructing StS data for the N2-N2 system, the kinetic data for the hybrid grouping model are calculated using the quasi-classical trajectory (QCT) method by sampling states for trajectory within the groups. This general framework is called the Maximum-Entropy Quasi-Classical Trajectory (ME-QCT) method. The primary challenge associated with this method is that rates for reverse grouped reactions cannot be obtained through detailed balance at a group level, due to the variation of group internal temperatures. To construct the full model for N2-N2 grouped kinetics using the ME-QCT method, detailed balance is invoked at the microscopic level, allowing for the calculation of the full kinetic data from QCT. Results will be presented using the full ME-QCT model for the N2-N2 system in an isothermal and isochoric reactor simulation. In addition, simple CFD test cases for a one-dimensional standing shock and for a quasi-one-dimensional nozzle will be used for demonstration of the ME-QCT method. This method allows for the calculation of non-equilibrium behavior for the N2-N2 system without the prohibitive cost of a full StS simulation. Moreover, it enables the construction of a unified model for the dissociating and recombining non-equilibrium flows.
Here, we investigate properties of lower hybrid drift waves (LHDWs) near and inside the electron diffusion regions in 17 magnetopause and 9 magnetotail reconnection events using Magnetospheric MultiScale (MMS) mission observations. Our analysis show that LHDW type depend on the electron beta, as electron beta increases LHDWs become more electromagnetic in nature. The energy transfer from electromagnetic fields to particles is higher in electrostatic LHDWs and it is largely in parallel direction with respect to the local magnetic field. Linear dispersion analysis shows that electrostatic LHDWs are perpendicular propagating while electromagnetic waves propagate in oblique directions and the normalized wavenumber of all LHDW types falls within 0.5–0.8 range. A simple estimate on the LHDW nonlinear saturation suggests a possibly important roles played by these waves in supporting the reconnection electric field.
Quenching of the emission of both the polystyrene monomer and the excimer for a series of varying composition copolymer films of styrene and 2-(2'-hydroxy-5'-vinylphenyl)-2H-benzotriazole is reported. The preponderance of quenching for both the monomer and excimer emissions is due to interception of the migrating excitation at the quencher site, although additional quenching results via long-range dipole-dipole energy transfer from the monomer and excimer traps to the quencher trap. The quenching of the monomer fluorescence and phosphorescence and that of the excimer fluorescence were found to be temperature independent over the ranges 14-58 and 191-296 K, respectively. Most significantly, it is concluded that the energy migration process is temperature independent over the range 14-296 K.
Intensity and lifetime quenching of the polystyrene monomer and excimer fluorescence emission by a pendant quencher have been studied in the solid state and in solution for a series of copolymers of styrene and 2-(2-prime-hydroxy-5-prime-vinylphenyl)-2H-benzotriazole. Two mechanisms of quenching have been identified. One involves interception of the migrating monomer excitation by the quencher, and the other involves a single-step Foerster energy-transfer process from the excimer traps to a quencher. The relative efficiencies of these two quenching mechanisms in the solid state and in solution have been compared and related to the efficiency of electronic energy migration. An estimate of the excimer trap concentration in solid polystyrene is also reported.
Abstract The demands of a sustainable chemical industry are a driving force for the development of heterogeneous catalytic platforms exhibiting facile catalyst recovery, recycling, and resilience to diverse reaction conditions. Homogeneous‐to‐heterogeneous catalyst transitions can be realized through the integration of efficient homogeneous catalysts within porous matrices. Herein, we offer a versatile approach to understanding how guest distribution and evolution impact the catalytic performance of heterogeneous host–guest catalytic platforms by implementing the resonance energy transfer (RET) concept using fluorescent model systems mimicking the steric constraints of targeted catalysts. Using the RET‐based methodology, we mapped condition‐dependent guest (re)distribution within a porous support on the example of modular matrices such as metal–organic frameworks (MOFs). Furthermore, we correlate RET results performed on the model systems with the catalytic performance of two MOF‐encapsulated catalysts used to promote CO 2 hydrogenation and ring‐closing metathesis. Guests are incorporated using aperture‐opening encapsulation, and catalyst redistribution is not observed under practical reaction conditions, showcasing a pathway to advance catalyst recyclability in the case of host–guest platforms. These studies represent the first generalizable approach for mapping the guest distribution in heterogeneous host–guest catalytic systems, providing a foundation for predicting and tailoring the performance of catalysts integrated into various porous supports.
Abstract The demands of a sustainable chemical industry are a driving force for the development of heterogeneous catalytic platforms exhibiting facile catalyst recovery, recycling, and resilience to diverse reaction conditions. Homogeneous‐to‐heterogeneous catalyst transitions can be realized through the integration of efficient homogeneous catalysts within porous matrices. Herein, we offer a versatile approach to understanding how guest distribution and evolution impact the catalytic performance of heterogeneous host–guest catalytic platforms by implementing the resonance energy transfer (RET) concept using fluorescent model systems mimicking the steric constraints of targeted catalysts. Using the RET‐based methodology, we mapped condition‐dependent guest (re)distribution within a porous support on the example of modular matrices such as metal–organic frameworks (MOFs). Furthermore, we correlate RET results performed on the model systems with the catalytic performance of two MOF‐encapsulated catalysts used to promote CO 2 hydrogenation and ring‐closing metathesis. Guests are incorporated using aperture‐opening encapsulation, and catalyst redistribution is not observed under practical reaction conditions, showcasing a pathway to advance catalyst recyclability in the case of host–guest platforms. These studies represent the first generalizable approach for mapping the guest distribution in heterogeneous host–guest catalytic systems, providing a foundation for predicting and tailoring the performance of catalysts integrated into various porous supports.
The paper presents a new electron gas intermolecular NH3-He potential determined by the Hartree-Fock results of Davis, Boggs, and Mehrotra (1979) with semiempirical long-range induction and dispersion terms. The resulting potential agrees with beam scattering and pressure broadening measurements; it was also found that the quadrupole induced dipole interaction is not as effective as the short range anisotropy. It was concluded that discrepancies remain in the quantitative description of energy transfer in the NH3-He system; discrepancies result from improper consideration of the dependence of cross-sections on degenerate magnetic quantum levels in the experimental investigation.
Ultraviolet emission produced by photoexcitation of NO at 50-80 nm is observed using synchrotron radiation as a light source. The emission increases at an excitation wavelength corresponding to the ionization potential of the NO(+) (a) state. The emission spectra at several excitation wavelengths are dispersed and identified to be mainly the NO(gamma) band. The dependence of emission intensity on gas pressure and delay time indicates that the emission is produced by a secondary reaction, which is attributed to the energy transfer from NO(+) (a) to NO.
An investigation of the behavior of the power-conditioning system as a whole is a necessity to ensure the integrity of the aggregate system in the case of space applications. An approach for conducting such an investigation is considered. A description is given of the application of a general digital analog simulator program to the study of an aggregate power-conditioning system which is being developed for use on the International Ultraviolet Explorer spacecraft. The function of the direct energy transfer system studied involves a coupling of a solar array through a main distribution bus to the spacecraft electrical loads.
An intrinsic feature of turbulent flows is an enhanced rate of mixing and kinetic energy dissipation due to the rapid generation of small-scale motions from large-scale excitation. The transfer of kinetic energy from large to small scales is commonly attributed to the stretching of vorticity by the strain rate, but strain self-amplification also plays a role. Previous treatments of this connection are phenomenological or inexact, or cannot distinguish the contribution of vorticity stretching from that of strain self-amplification. In this Letter, an exact relationship is derived which quantitatively establishes how intuitive multiscale mechanisms such as vorticity stretching and strain self-amplification together actuate the interscale transfer of energy in turbulence. Further, numerical evidence verifies this result and uses it to demonstrate that the contribution of strain self-amplification to energy transfer is higher than that of vorticity stretching, but not overwhelmingly so.
Crystalline metal-organic frameworks (MOFs) can assemble chromophoric molecules into a wide range of spatial arrangements, which are controlled by the MOF topology. Like natural light-harvesting complexes (LHCs), the precise arrangement modulates interchromophoric interactions, in turn determining excitonic behavior and migration dynamics. To unveil the key factors that control efficient exciton displacements within MOFs, we first developed linkers with low electronic symmetry (as defined by large transition dipoles) and then assembled them into MOFs. These linkers possess extended conjugation along one molecular axis, engendering low optical bandgaps and improved oscillator strength for their lowest-energy transition (S 0 → S 1 ). This enhances absorption-emission spectral overlap and boosts the efficiency of Forster resonance energy transfer, which was observed experimentally by a sizable decrease in emission quantum yield (QY), accompanied by a faster population decay profile. We find that MOFs that orient these elongated linkers along their asymmetric pore channel, e.g., the hexagonal pores in an xly network, manifested >50% decrease in their emission QY with faster decay profiles relative to their corresponding solution dissolved linkers. This is due to an efficient migration of photogenerated excitons at the crystallite peripheral sites to internal sites, which was facilitated by polarized absorption-emission overlap among the parallelly aligned linkers. In contrast, symmetric MOFs, such as those with sqc-a topological net, orient elongated linkers along two perpendicular crystal axes, which hinders efficient exciton migration. This study underscores that MOFs are promising to develop artificial LHCs, but that to achieve an efficient exciton displacement, appropriate topology-guided assembly is required to fully realize the true potential of linkers with low electronic symmetry.
In the field of supramolecular chemistry, host- guest systems have been extensively explored to encapsulate a wide range of substrates, owing to emerging functionalities in nano-confined space that cannot be achieved in dilute solutions. However, host-guest chemistry is still limited to encapsulation of small guests. Herein, we construct a water-soluble metallo-supramolecular hexagonal prism with a large hydrophobic cavity by anchoring multiple polyethylene glycol chains onto the building blocks. Then, assembled prisms are able to encapsulate quantum dots (QDs) with diameters of less than 5.0 nm. Furthermore, we find that the supramolecular cage around each QD strongly modifies the photophysics of the QD by universally increasing the rates of QD relaxation processes via ultrafast electron and vibrational energy transfer. In conclusion, taken together, these efforts expand the scope of substrates in host-guest systems and provide a new approach to tune the optical properties of QDs.
Polymer nanocomposites offer design solutions to control and tune optical, conductive, topological, and thermomechanical properties of advanced and multifunctional materials. Because of their ubiquitous nature, methodologies to diagnose failure or structural changes in the nanocomposites are of significant interest. Herein, we report a nanocomposite system loaded with quantum dots and coumarin-modified carbon nanotubes that transduce mechanical force into fluorescence at a strain, for the first time, as low as 7.5%. Our comprehensive studies detail the optical, morphological, and thermomechanical properties of these nanocomposites to establish the fundamental reason behind the activation of fluorescence. Here our results indicate that bare carbon nanotubes can irreversibly quench the fluorescence from quantum dots and that the coumarin-modified carbon nanotubes mitigate the quenching through Förster Resonance Energy Transfer. Next, the application of force to the sample changes the quantum dot-carbon nanotube spacing as well as the carbon nanotube morphology to activate fluorescence in the nanocomposite. Overall, this force activation of fluorescence can serve as a general strategy for the development of a new class of mechano-responsive nanocomposites that impart polymeric materials with desirable functionalities including damage sensing and mechanical strength.
A multiband model for the absorption coefficient of atomic hydrogen-helium plasmas is constructed which includes continuum and line contributions. Emission from 28 stronger lines of 106 that have been screened is considered, of which 21 are from hydrogen and 7 belong to helium, with reabsorption due to line-line, line-continuum overlap accurately accounted for. The model is utilized in the computation of intensities and fluxes from shock-heated slabs of 85% H2-15% He mixtures for slab thicknesses from 1 to 30 cm, temperature from 10,000 to 20,000 K, and for different densities. In conjunction with the multiband model, simple numerical schemes have been devised which provide a quick and comprehensive way of computing radiative energy transfer in nonisothermal and nongrey gases.
The design of earth-abundant molecular photosensitizers with desirable photophysical properties and good excited-state reactivity is critical for sustainable photochemical applications. Herein, we report a new family of three-coordinate heteroleptic Cu(I) complexes supported by monoanionic salicylaldimine (N^O) chelating ligands and aryl isocyanides. By systematically tuning the steric bulk on each ligand, we establish clear structure–property relationships that govern the excited-state lifetimes and photocatalytic performance metrics of these complexes. Increasing steric congestion on the salicylaldimine ligand, which contributes to the HOMO, results in faster nonradiative decay and shortens excited-state lifetimes. In contrast, introducing steric bulk on the isocyanide ligand, where the LUMO is primarily localized, suppresses nonradiative decay, most likely by inhibiting excited-state geometric relaxation, thereby extending the lifetime up to 375 ns. These photophysical trends correlate directly with performance in triplet–triplet energy transfer (TTET) photocatalysis, where longer-lived complexes enable faster E/Z isomerization of trans-stilbene. This work demonstrates that remote steric modulation of ligand frameworks offers a simple yet powerful strategy for tuning the excited-state dynamics and catalytic properties of this new class of Cu(I) photosensitizers.