Energy Relaxation Processes Research Articles

The Influence of Filler Particle Size on the Strength Properties and Mechanical Energy Dissipation Capacity of Biopoly(Ethylene Terephthalate) BioPET/Eggshell Biocomposites

This work aims to evaluate how the particle size of a waste filler in the form of eggshells changes the mechanical properties of biopoly(ethylene terephthalate) (bioPET). BioPET was modified with three different waste fractions: 1.60–3 mm—large particles; 1.60–1 mm—medium particles; 1 mm–200 μm—small particles. Waste filler was added to the biopolymer matrix in the amount of 10 wt.%. Static tensile tests, as well as bending and impact tests, were carried out to assess the strength properties of the waste-enriched materials. Dissipation energy changes and relaxation processes were observed and evaluated by means of a low-cycle dynamic test. Waste particles were shown to be an effective modifier of bioPET by increasing its stiffness (all particle sizes) and strength (the smallest ones). Studies of the wetting angle and mechanical energy dissipation in the first hysteresis loops indicate the better adhesion of small particles to the biopolymer and their greater ability to dissipate mechanical energy.

Progress in electron energy modeling for plasma flows and discharges

A novel formulation of the electron energy relaxation terms is presented here, which is applicable to plasma flows and discharges wherein the electron temperature could be higher or lower than the gas temperature. It is demonstrated that the electron energy losses due to inelastic collisions can be expressed as a function of only two species-dependent parameters: the reduced electric field and the reduced electron mobility. This formulation is advantageous over previous ones, being simpler to implement and more accurate when experimental data of the reduced electric field and reduced mobility are available. Curve fits to empirical data of these two properties are outlined here for all important air molecular species. The approach accounts for all inelastic electron energy relaxation processes without needing individual cross sections or rates, reducing potential errors associated with independently handling each process. Several test cases are presented to validate the proposed electron energy source terms including reentry plasma flows for which the electron temperature is less than the gas temperature, as well as discharges in which the electron temperature reaches values in excess of 30 eV. In all cases, the agreement with experimental data is observed to be very good to excellent, significantly surpassing prior electron energy models for plasma flows.

Adsorption induced bipolar excitation at semiconductor surface

Adsorption on metal surfaces has been shown to lead to chemisorption induced electronic excitation but direct experimental evidence of chemisorption induced excitation on semiconductor surfaces is still missing. Here, we design and use high-quality Silicon (Si) p-n diodes to in-situ probe the charge transfer process taking place during vapor and liquid phase chemisorption of iodine molecules on H-Si (100) surface. We find that the diodes can generate electricity and feed an external circuit during the chemisorption process, demonstrating chemisorption-induced electron and hole generation and the means to electrically monitor the process. A bipolar semiconductor electrochemical model where a single semiconductor surface hosts the spontaneous oxidation (electron injection) and reduction (hole injection) reactions simultaneously on its conduction and valence bands without any electrolytes is proposed to explain the observations. Our work provides new insight on the energy relaxation processes of chemisorption and also calls for further studies on the observed chemovoltaic effect. Overall, the results indicate a possibility for developing electrolyte-free vapor phase chemical energy-to-electricity converters and detectors.

Time-resolved characteristics of a nanosecond pulsed multi-hollow needle plate packed bed dielectric barrier discharge

In this paper, self-designed multi-hollow needle electrodes are used as a high-voltage electrode in a packed bed dielectric barrier discharge reactor to facilitate fast gas flow through the active discharge area and achieve large-volume stable discharge. The dynamic characteristics of the plasma, the generated active species, and the energy transfer mechanisms in both positive discharge (PD) and negative discharge (ND) are investigated by using fast-exposure intensified charge coupled device (ICCD) images and time-resolved optical emission spectra. The experimental results show that the discharge intensity, number of discharge channels, and discharge volume are obviously enhanced when the multi-needle electrode is replaced by a multi-hollow needle electrode. During a single voltage pulse period, PD mainly develops in a streamer mode, which results in a stronger discharge current, luminous intensity, and E/N compared with the diffuse mode observed in ND. In PD, as the gap between dielectric beads changes from 0 to 250 μm, the discharge between the dielectric bead gap changes from a partial discharge to a standing filamentary micro-discharge, which allows the plasma to leave the local area and is conducive to the propagation of surface streamers. In ND, the discharge only appears as a diffusion-like mode between the gap of dielectric beads, regardless of whether there is a discharge gap. Moreover, the generation of excited states and is mainly observed in PD, which is attributed to the higher E/N in PD than that in ND. However, the generation of the radical in ND is higher than in PD. It is not directly dominated by E/N, but mainly by the resonant energy transfer process between metastable and . Furthermore, both PD and ND demonstrate obvious energy relaxation processes of electron-to-vibration and vibration-to-vibration, and no vibration-to-rotation energy relaxation process is observed.

Density Functional Theory Calculations on Fluorescence-Enhanced Mechanisms of the Optical Sensor for Zinc Ions, ADPA.

N-(9-anthracenylmethyl)-N-(2-pyridinylmethyl)-2-pyridinemethanamine (ADPA) as a specific ion sensor for Zn2+ has been widely applied. Although the photo-induced electron transfer (PET) mechanism was proposed previously, its fluorescence-enhanced effect still remains somewhat ambiguous, according to unknown influences of non-radiative energy decay pathways, such as intersystem crossing and internal conversion. Herein, a thorough study using density functional theory has been performed for low-lying electronic states of the ADPA monomer and hydrated ADPA-Zn2+ complex. Based on interfragment charge transfer analyses, we quantitatively calculated the amount of transferred electrons in the monomer and complex, providing solid evidences for the PET mechanism and in line with the conclusion of frontier molecular orbital analyses. Moreover, the ISC process of S1→T2 was confirmed to play a considerable role in the excitation energy relaxation process of the ADPA monomer, but this influence was significantly suppressed in the hydrated ADPA-Zn2+ complex. These results provide additional clues for the design of new metal ion-specific fluorescence probes.

On the Statistical Regime, Coherence versus Incoherence and Ergodicity of Quantum Vibrational Trajectories in Soft Condensed Molecular Systems.

A theoretical-computational procedure, recently proposed for modelling Vibrational Energy Relaxation (VER) processes of a molecule (Quantum Center, QC) embedded in a complex atomic-molecular system, is extended and applied for analyzing in detail the features of the QC density matrix (DM) temporal evolution. The results, obtained using aqueous azide ion as a case study, show the total lack of coherence in the DM, when the system is prepared to be initially in a pure vibrational eigenstate. This finding is fully in line with the statistical interpretation of the process typically adopted also in the experimental studies where the relaxation processes are all described within the typical schemes of chemical kinetics. Consistently, when the initial vibrational state corresponds to an eigenstate mixture, although initially coherent, the DM relaxes to a fully incoherent condition with a mean lifetime related to the one of the diagonal elements relaxation. These specific DM features turn out to be essentially governed by the thermal equilibrium condition of the atomic-molecular classical coordinates which drive the ensemble of the quantum-trajectories toward the observed statistical regime. Finally, from the analysis of a single long timescale quantum vibrational trajectory it also clearly emerges its ergodic behaviour.

Sub-bandgap optical absorption processes in 300-nm-thick Al1−xInxN alloys grown on a c-plane GaN/sapphire template

We investigate the sub-bandgap optical absorption (SOA) in 300-nm-thick Al1−xInxN alloys used in cladding layers of edge-emitting laser diodes and distributed Bragg reflectors of vertical-cavity surface-emitting lasers. Al1−xInxN alloys, with indium content x ranging from 0.114 to 0.185, were grown by metal-organic chemical vapor deposition on a c-plane GaN/sapphire template. SOAs on 300-nm-thick thin films were characterized using photothermal deflection spectroscopy (PDS). Thermal emission, such as nonradiative recombination with phonon emission, is the dominant energy relaxation process occurring after SOA in Al1−xInxN alloys. The absorption coefficient of the SOA was estimated to be 0.6–7.0 × 103 cm−1 in these samples by combining PDS and spectroscopic ellipsometry. The drastic increase in the SOA, when x exceeded the lattice-matched composition of the GaN/sapphire template, indicates that impurities, vacancy-type defects, and their complexes with increasing x are possible candidates that result in SOA in Al1−xInxN alloys.

A detailed analysis on the heat generated inside c-Si solar cell

The heat generated inside solar cells is one of the important factors influencing the operational stability of a photovoltaic system composed of solar cells. In this work, based on the influencing factors of four main heat-generated mechanisms inside c-Si solar cells, i.e., the energy relaxation process of the hot carrier, Joule heat, recombination heat, and Peltier and Thomson effects, the distribution features of the heat generated by each mechanism are first discussed, and then, considering two common working conditions of c-Si solar cells in module form, i.e., the variations of environmental temperature and output voltage, the changing rules of the distributions of heat generated by different mechanisms are analyzed. The general features of the heat distributions of c-Si solar cells are that the obviously absorbed and released heat only exists in the regions near the front and back surfaces; the four mechanisms all release heat in the narrow n region close to the front surface; and Peltier and Thomson effects are the only mechanism of absorbed heat in the wide p region. The offset effects between released and absorbed heat make the total heat generated by the four mechanisms very small in the wide p region. With the environmental temperature increasing, the heat distribution features of each heat mechanism will remain unchanged, and except for the heat generated by the energy relaxation of the hot carrier, the released and absorbed heat generated by other mechanisms will increase in the whole c-Si active layer. With the output voltage increasing from 0 to 0.68 V, aside from the heat distribution of the energy relaxation of the hot carrier, the distributions of heat generated by other mechanisms show obvious threshold voltage effects, and only when the output voltage is larger than the threshold voltage will the heat distributions of different mechanisms be significantly changed by the variations of the output voltage.

The comprehensive investigation of barrier layers on power loss mechanisms in AlGaN/GaN HEMT structures

The electron relaxation mechanism of the electrons in the pseudo triangle quantum well located in the Al0.3Ga0.7N/GaN heterostructure interface grown by the Molecular Beam Epitaxy (MBE) is studied by Shubnikov de-Haas (SdH) oscillations. Four different sample types were used in the experiments; the carrier density in the quantum well is the same for all samples, whereas the top layer structures are different. The effects of a spacer layer placed between the barrier layer and the quantum well layer, a doped barrier layer placed behind the undoped barrier layer, and a passivation layer placed as a top layer on the energy relaxation processes of the carriers in the quantum well were investigated. The SdH oscillation measurements were carried out under a magnetic field of up to 11 T at a temperature range of 1.8–20 K. The electron temperatures and energy relaxation mechanisms are obtained by comparing the change in the relative amplitude of SdH oscillations in different applied electric fields and lattice temperatures. It is deduced that the samples with a passivation layer and doped barrier layer have higher electron temperatures at lower applied electric fields. The hot electrons relax with acoustic phonon scattering for these samples, including deformation and piezoelectric interactions in the low-temperature region determined theoretically. However, the hot electrons relax with acoustic phonon scattering for samples with spacer layer and spacer/passivation layers in the high-temperature region determined theoretically. Furthermore, it was observed that the spacer and passivation layers lead to faster relaxation of hot electrons.

The role of IR inactive mode in W(CO)6 polariton relaxation process

Abstract Vibrational polaritons have shown potential in influencing chemical reactions, but the exact mechanism by which they impact vibrational energy redistribution, crucial for rational polariton chemistry design, remains unclear. In this work, we shed light on this aspect by revealing the role of solvent phonon modes in facilitating the energy relaxation process from the polaritons formed of a T 1u mode of W(CO)6 to an IR inactive E g mode. Ultrafast dynamic measurements indicate that along with the direct relaxation to the dark T 1u modes, lower polaritons also transition to an intermediate state, which then subsequently relaxes to the T 1u mode. We reason that the intermediate state could correspond to the near-in-energy Raman active E g mode, which is populated through a phonon scattering process. This proposed mechanism finds support in the observed dependence of the IR-inactive state’s population on the factors influencing phonon density of states, e.g., solvents. The significance of the Raman mode’s involvement emphasizes the importance of non-IR active modes in modifying chemical reactions and ultrafast molecular dynamics.

Dispersion control by using a bulky surfactant medium in the LB films for the enhancement of linearly polarized luminescence of Eu complexes

Abstract The ff transition of lanthanide ions such as Eu in the complex appears as unique energy relaxation process as luminescence after the intramolecular energy transfer from the photo-excitation of the ligand with π-electronic system. The Langmuir-Blodgett (LB) film consisting of Eu and amphiphilic naphtoic acids (NaphC15) induced the linearly polarized luminescence (LPL) with a medium, stearic acid (SA), to isolate the luminescence component by the layer structure and to keep the softness at the monolayer depositions on the quartz substrate as reported previously. Here, we used a bulky medium, 3-methyl-4-penthadecyl benzoic acid (MPBA), instead of SA, and found the Eu-NaphC15 in the LB film places more independently resulting in the 4-fold high quantum yields compared with previous system. The structures of LB films of Eu-NaphC15 with MPBA were elucidated by the measurement of synchrotron XRD and XPS. Various electronic spectra were quantitatively observed to discuss the effect molecular aggregation through much/less ππ-interaction of NaphC15 for the intensified LPL in the films.

Thermalization of open quantum systems using the multiple-Davydov- D2 variational approach

Numerical implementation of an explicit phonon bath requires a large number of oscillator modes in order to maintain oscillators at the initial temperature when modeling energy relaxation processes. An additional thermalization algorithm may be useful in controlling the local temperature. In this paper we extend our previously proposed thermalization algorithm [M. Jaku\v{c}ionis and D. Abramavi\v{c}ius, Phys. Rev. A 103, 032202 (2021) ] to be used with the numerically exact multiple-Davydov-D2 trial wave function for simulation of relaxation dynamics and spectroscopic signals of open quantum systems using the time-dependent Dirac-Frenkel variational principle. By applying it to the molecular aggregate model, we demonstrate how the thermalization approach significantly reduces the numerical cost of simulations by decreasing the number of oscillators needed to explicitly simulate the aggregate's environment fluctuations while maintaining correspondence to the exact population relaxation dynamics. Additionally, we show how the thermalization can be used to find the equilibrium state of the excited molecular aggregate, which is necessary for simulation of the fluorescence and other spectroscopic signals. The thermalization algorithm we present offers the possibility to investigate larger system-bath models than was previously possible using the multiple-Davydov-D2 trial wave function and local heating effects in molecular complexes.

Thermalization of the Kerr index of refraction in acetone and methanol using femtosecond pump-probe scattering spectroscopy

Femtosecond time-resolved pump-probe scattering is used to temporally investigate the index thermalization Δn(t) of the molecular motions associated with the Kerr nonlinear index n2. This is done using an intense 300 fs 1034 nm pump pulse and temporally probed by a 517 nm and supercontinuum pulse in acetone and methanol. The optically pumped molecular states change the index of refraction and through the processes of Raman and Rayleigh scattering are shown to engage in a 4-step energy relaxation process. Here, the pump first initiates the Kerr effect as well as populate resonant vibrational molecular motions, which act as a “mother” energy state. The electronic component of the Kerr effect is shown to couple with these vibrational modes through the process of Born-Oppenheimer coupling, which can be measured through the Raman scattering of the probe. The “mother” coupled state then decays into “daughter” anharmonic non-resonant states, which then further decay into “granddaughter” and thermal bath states. The population of these states alter the index of refraction in time, Δn(t), and can be measured through the changing in the probe beam’s Rayleigh scattering. This thermalization process takes ∼5.5 ps in acetone and ∼3.7 ps in methanol. The scattering signals from each Δn(t) thermalization stage in the localized region, (“mother”, to “daughter”, to “granddaughter”, to the bath states, to the ground state), are fitted to theoretical decay equations that show the rise and fall times of the energy decay routes.

Prediction of hot zone-center optical phonons in laser-irradiated molybdenum disulfide with a semiconductor multitemperature model

A previous multitemperature model (MTM) resolving phonon temperatures at the polarization level and measurements have uncovered remarkable nonequilibrium among different phonon polarizations in laser-irradiated graphene and metals. Here, we develop a semiconductor-specific MTM (SC-MTM) by including electron-hole pair generation, diffusion, and recombination, and show that a phonon polarization-level model does not yield observable polarization-based nonequilibrium in laser-irradiated molybdenum disulfide (${\mathrm{MoS}}_{2}$). In contrast, appreciable nonequilibrium is predicted between zone-center optical phonons and the other modes. The momentum-based nonequilibrium ratio is found to increase with decreasing laser spot size and interaction with a substrate. This finding is relevant to the understanding of the energy relaxation process in two-dimensional optoelectronic devices and Raman measurements of thermal transport.

Giant Angular Nernst Effect in the Organic Metal α-(BEDT-TTF)2KHg(SCN)4

We have detected a large Nernst effect in the charge density wave state of the multiband organic metal α-(BEDT-TTF)2KHg(SCN)4. We find that apart from the phonon drag effect, the energy relaxation processes that govern the electron–phonon interactions and the momentum relaxation processes that determine the mobility of the q1D charge carriers have a significant role in observing the large Nernst signal in the CDW state in this organic metal. The emphasised momentum relaxation dynamics in the low field CDW state (CDW0) is a clear indicator of the presence of a significant carrier mobility that might be the main source for observation of the largest Nernst signal. The momentum relaxation is absent with increasing angle and magnetic field, i.e., in the high-field CDW state (CDWx) as evident from the much smaller Nernst effect amplitude in this state. In this case, only the phonon drag effect and electron–phonon interactions are contributing to the transverse thermoelectric signal. Our findings advance and change previous observations on the complex properties of this organic metal.

Surface Properties, Interface Events and Energy Relaxation Processes in Nanoassemblies Based on Ag-In-S/ZnS Quantum Dots and Porphyrins

Surface Properties, Interface Events and Energy Relaxation Processes in Nanoassemblies Based on Ag-In-S/ZnS Quantum Dots and Porphyrins

Internal Energy Relaxation Processes and Bulk Viscosities in Fluids

Internal energy relaxation processes in fluid models derived from the kinetic theory are revisited, as are related bulk viscosity coefficients. The apparition of bulk viscosity coefficients in relaxation regimes and the links with equilibrium one-temperature bulk viscosity coefficients are discussed. First, a two-temperature model with a single internal energy mode is investigated, then a two-temperature model with two internal energy modes and finally a state-to-state model for mixtures of gases. All these models lead to a unique physical interpretation of the apparition of bulk viscosity effects when relaxation characteristic times are smaller than fluid times. Monte Carlo numerical simulations of internal energy relaxation processes in model gases are then performed, and power spectrums of density fluctuations are computed. When the energy relaxation time is smaller than the fluid time, both the two temperature and the single-temperature model including bulk viscosity yield a satisfactory description. When the energy relaxation time is larger than the fluid time, however, only the two-temperature model is in agreement with Boltzmann equation. The quantum population of a He-H2 mixture is also simulated with detailed He-H2 cross sections, and the resulting bulk viscosity evaluated from the Green–Kubo formula is in agreement with the theory. The impact of bulk viscosity in fluid mechanics is also addressed, as well as various mathematical aspects of internal energy relaxation and Chapman–Enskog asymptotic expansion for a two-temperature fluid model.

Reheating after relaxation of large cosmological constant

We present a cosmological model of an early-time scenario that incorporates a relaxation process of the would-be large vacuum energy, followed by a reheating era connecting to the standard hot big bang universe. Avoiding fine-tuning the cosmological constant is achieved by the dynamics of a scalar field whose kinetic term is modulated by an inverse power of spacetime curvature [1,2]. While it is at work against radiative corrections to the dark energy, this mechanism alone would wipe out not only the vacuum energy but also all other matter contents. Our present work aims to complete the scenario by exploiting a null-energy-condition violating sector whose energy is eventually transferred to a reheating sector. We provide an explicit example of this process and thus a concrete scenario of the cosmic onset that realizes the thermal history of the Universe with a negligible cosmological constant.

Effects of hot phonons and thermal stress in micro-Raman spectra of molybdenum disulfide

Micro-Raman spectroscopy has become an important tool in probing thermophysical properties in functional materials. Localized heating by the focused Raman excitation laser beam can produce both stress and local nonequilibrium phonons in the material. Here, we investigate the effects of hot optical phonons in the Raman spectra of molybdenum disulfide and distinguish them from those caused by thermally induced compressive stress, which causes a Raman frequency blue shift. We use a thermomechanical analysis to correct for this stress effect in the equivalent lattice temperature extracted from the measured Raman peak shift. When the heating Gaussian laser beam is reduced to 0.71 μm, the corrected peak shift temperature rise is 17% and 8%, respectively, higher than those determined from the measured peak shift and linewidth without the stress correction, and 32% smaller than the optical phonon temperature rise obtained from the anti-Stokes to Stokes intensity ratio. This nonequilibrium between the hot optical phonons and the lattice vanishes as the beam width increases to 1.53 μm. Much less pronounced than those reported in prior micro-Raman measurements of suspended graphene, this observed hot phonon behavior agrees with a first-principles based multitemperature model of overpopulated zone-center optical phonons compared to other optical phonons in the Brillouin zone and acoustic phonons of this prototypical transition metal dichalcogenide. The findings provide detailed insight into the energy relaxation processes in this emerging electronic and optoelectronic material and clarify an important question in micro-Raman measurements of thermal transport in this and other two-dimensional materials.

Disentangling the Ultrafast Nonlinear Optical Behavior of Plasmonic Resonances Near the Interband Transition

The photoexcitation of plasmonic nanostructures with ultrashort laser pulses allows for elucidating the mechanisms underlying the ultrafast nonlinear optical response of such systems, gaining insight into the fundamental processes triggered by light absorption at the nanoscale. To date, the complex temporal and spectral features of the photoinduced response are not fully understood, especially when the photon energies are close to the interband transitions of the metallic medium. Herein, the effects of photoexcitation of plasmonic nanostructures are studied by resorting to a combinaion of broadband transient absorption spectroscopy and semiclassical nonlinear simulations of the energy relaxation processes following illumination. The proposed approach enables an in‐depth disentanglement of all the contributions to the ultrafast transient optical response of supported gold nanocrystals. From these methods, the apparent transient blue shift of the localized plasmon resonance observed in the pump–probe signals is rationalized as an interplay between different and spectrally dispersed permittivity modulations, instead of a simple negative permittivity change, as it could be concluded based on the Fröhlich condition. The results provide a comprehensive understanding of the thermo‐modulational nonlinearities of plasmonic nanostructures exhibiting resonances close to the interband transition threshold.