Energy Relaxation Research Articles

Hot-Electron Microwave Noise and Energy Relaxation in (Be)MgZnO/ZnO Heterostructures

Pulsed hot-electron microwave noise measurements of the (Be)MgZnO/ZnO heterostructures are presented in this work. The heterostructures of different barrier thicknesses and different bulk electron densities in ZnO layer are compared. Capacitance–voltage (C–V) measurements reveal the decrease in the two-dimensional electron gas (2DEG) peak in electron density profile at the Zn-polar BeMgZnO/ZnO interface as the BeMgZnO barrier layer thickness decreases. For thin-barrier heterostructures, the peak disappears and only the bulk electron density is resolved in C–V measurements. The excess noise temperature at ∼10 GHz in thick-barrier heterostructures is noticeably higher (∼10 times) compared to thin-barrier heterostructures, which is attributed to the strong noise source in the contacts of the former. In the case of thin-barrier heterostructures, at electric fields above ∼10 kV/cm and electron density ≳1×1017cm−3, strong noise source is resolved, which was also observed earlier in the Ga-doped ZnO films due to the formation of self-supporting high-field domains. However, for the low electron densities (≲6 ×1016 cm−3), the aforementioned noise source is not observed, which suggests the importance of a deep ZnO/GaN interface with 2DEG for power dissipation. The hot-electron temperature dependence on the dissipated power of those low-electron-density heterostructures is similar to that of O-polar ZnO/MgZnO. The estimated electron energy relaxation time in ZnO/MgZnO is ∼0.45 ps ± 0.05 ps at dissipated electrical power per electron of ∼0.1 nW/el and approaches ∼0.1 ps as the dissipated power is increased above ∼10 nW/el.

Direct Observation of the Mutual Coupling Effect in the Protein-Water-Glycerol Mixture by Combining Neutron Scattering and Selective Deuteration.

Numerous studies have discussed the impact of cosolvents on the structure, dynamics, and stability of proteins in aqueous solutions. However, the dynamics of cosolvents in the protein-water-cosolvent ternary system is largely unexplored in experiments due to technical difficulty. Consequently, a comprehensive understanding of the interplay among proteins, water, and cosolvents is still lacking. Here, we employed selective deuteration and neutron scattering techniques to characterize the individual motions of each component in the protein/water/glycerol (GLY) mixture across various temperatures. The consistent dynamic onset temperatures and the correlation between the MSD of the protein and the viscosity of solvents revealed the mutual coupling effects among the three components. Furthermore, our experimental and simulation results showed that the hydrogen bond relaxation energy barrier in the ternary system is ∼43 kJ/mol, whereas in the protein-water binary system it is merely ∼35 kJ/mol. Therefore, we suggest that GLY can enhance hydrogen bond interactions in the ternary system through the mutual coupling effect, thereby serving as one of the protective mechanisms of protein preservation by GLY.

Kinetic simulations of low-pressure inductively coupled plasma: an implicit electromagnetic PIC/MCC model with the ADI-FDTD method

Low-pressure inductively coupled plasma (ICP) is promising for space electric propulsion. For the first time, an implicit electromagnetic particle-in-cell Monte Carlo collision model based on the alternating-direction-implicit finite-difference time-domain (ADI-FDTD) method is developed to investigate low-pressure xenon plasma characteristics of a miniature ICP source. The induced simulated electric field is well consistent with that calculated by the finite element method, indicating that this method can provide an accurate estimation of the electromagnetic field. The simulation time step used in the ADI-FDTD method is no longer restricted by the Courant–Friedrichs–Lewy constraints. Compared with the FDTD method, the ADI-FDTD method increases the size of the time step and significantly improves computational efficiency. The method is validated by comparing the simulated and measured electron density and plasma potential profile and reasonable agreement is reached. Therefore, the model is used to investigate the temporal and spatial distribution of plasma properties and the influence of the current amplitude of radio frequency (RF) coil, applied frequency of RF coil and neutral gas pressure on the plasma dynamics in the ionization chamber of a miniature gridded RF ion thruster. To explain the influence of the operating parameters, a concept called ‘the energy relaxation characteristics of electrons in response to the change of electric field’ is proposed and verified. The simulations also find that the oscillation frequency of plasma properties is twice the applied frequency of RF coil. The oscillation characteristics reveal the dynamic energy balance in the ICP. The experiment on the gridded RF ion thruster BHRIT-4 confirms the oscillation by measuring the plasma sheath potential.

Effect of compaction pressure on sinterability, microstructure and electrical behavior of Ba0.5Na0.48Sr0.02TiO3 system

The microstructure of electroceramics is a highly influencing factor to decide its functionality and applicability. Processing conditions used for the conversion of raw powder of electroceramics to the net product are playing a dominant role to modulate microstructure. In the present attempt, various compaction pressures (5 tons/cm2, 7 tons/cm2, and 9 tons/cm2) are used to densify the powder sample to the pellet. The effect of the pressure on sinterability, microstructure, and electrical behavior is systematically revealed. Ba0.5Na0.48Sr0.02TiO3 (BNST) with optimized composition has been prepared by the sol-gel combustion method. The structure is confirmed by X-ray diffraction and accompanied by Rietveld refinements. The compaction pressure effect on sinterability is systematically studied by revealing variation of relative density as a function of temperature at constant holding time as well as a function of holding time at a constant temperature. The final obtained relative density is found to be strongly affected by compaction pressure. Microstructural changes during the sintering process are closely monitored and found porosity, grain size, and grain size distribution are strongly affected by compaction pressure. That indirectly influenced electrical behavior. Relaxation frequency and activation energy of charge relaxation are also found to be varied with the compaction pressure of the powder samples.

Cross-over from pyrene to acene optical and electronic properties: a theoretical investigation of a series of pyrene derivatives fused with N-, S, and O-containing heterocycles.

Pyrene and acene derivatives are an important source of materials for optoelectronic device applications both as emitters and organic semiconductors. The mobility of major charge carriers is correlated with the coupling constants of the respective major charge carrier as well as the relaxation energies. Herein, we have applied range-separated density functionals for the estimation of said values. A series of five alkylated derivatives of pyrene laterally extended by heteroaromatic or phenyl groups were explored and contrasted to nascent pyrene, alkylated pyrene and tetracene. The ground state geometries along with absorption properties and relaxation energies are presented as well as a discussion of the suitability of the material toward hole and electron transport materials.

Transient-absorption spectroscopy of dendrimers via nonadiabatic excited-state dynamics simulations.

The efficiency of light-harvesting and energy transfer in multi-chromophore ensembles underpins natural photosynthesis. Dendrimers are highly branched synthetic multi-chromophoric conjugated supra-molecules that mimic these natural processes. After photoexcitation, their repeated units participate in a number of intramolecular electronic energy relaxation and redistribution pathways that ultimately funnel to a sink. Here, a model four-branched dendrimer with a pyrene core is theoretically studied using nonadiabatic molecular dynamics simulations. We evaluate excited-state photoinduced dynamics of the dendrimer, and demonstrate on-the-fly simulations of its transient absorption pump-probe (TA-PP) spectra. We show how the evolutions of the simulated TA-PP spectra monitor in real time photoinduced energy relaxation and redistribution, and provide a detailed microscopic picture of the relevant energy-transfer pathways. To the best of our knowledge, this is the first of this kind of on-the-fly atomistic simulation of TA-PP signals reported for a large molecular system.

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.

On the lack of compactness in the axisymmetric neo-Hookean model

Abstract We provide a fine description of the weak limit of sequences of regular axisymmetric maps with equibounded neo-Hookean energy, under the assumption that they have finite surface energy. We prove that these weak limits have a dipole structure, showing that the singular map described by Conti and De Lellis is generic in some sense. On this map, we provide the explicit relaxation of the neo-Hookean energy. We also make a link with Cartesian currents showing that the candidate for the relaxation we obtained presents strong similarities with the relaxed energy in the context of $\mathbb {S}^2$ -valued harmonic maps.

Transient IR spectroscopy of optically centrifuged CO2 (R186-R282) and collision dynamics for the J = 244-282 states.

Collisions of optically centrifuged CO2 molecules with J = 244-282 (Erot = 22 800-30 300 cm-1) are investigated with high-resolution transient IR absorption spectroscopy to reveal collisional and orientational phenomena of molecules with hyper-thermal rotational energies. The optical centrifuge is a non-resonant optical excitation technique that uses ultrafast, 800 nm chirped pulses to drive molecules to extreme rotational states through sequential Raman transitions. The extent of rotational excitation is controlled by tuning the optical bandwidth of the excitation pulses. Frequencies of 30 R-branch ν3 fundamental IR probe transitions are measured for the J = 186-282 states of CO2, expanding beyond previously reported IR transitions up to J = 128. The optically centrifuged molecules have oriented angular momentum and unidirectional rotation. Polarization-sensitive transient IR absorption of individual rotational states of optically centrifuged molecules and their collision products reveals information about collisional energy transfer, relaxation kinetics, and dynamics of rotation-to-translation energy transfer. The transient IR probe also measures the extent of polarization anisotropy. Rotational energy transfer for lower energy molecules is discussed in terms of statistical models and a comparison highlights the role of increasing energy gap with J and angular momentum of the optically centrifuged molecules.

Harnessing machine learning for efficient large-scale interatomic potential for sildenafil and pharmaceuticals containing H, C, N, O, and S.

In this study a cutting-edge approach to producing accurate and computationally efficient interatomic potentials using machine learning algorithms is presented. Specifically, the study focuses on the application of Allegro, a novel machine learning algorithm, running on high-performance GPUs for training potentials. The choice of training parameters plays a pivotal role in the quality of the potential functions. To enable this methodology, the "Solvated Protein Fragments" dataset, containing nearly 2.7 million Density Functional Theory (DFT) calculations for many-body intermolecular interactions involving protein fragments and water molecules, encompassing H, C, N, O, and S elements, is considered as the training dataset. The project optimizes computational efficiency by reducing the initial dataset size according to the intended application. To assess the efficacy of the approach, the sildenafil citrate, iso-sildenafil, aspirin, ibuprofen, mebendazole and urea, representing all five relevant elements, serve as the test bed. The results of the Allegro-trained potentials demonstrate outstanding performance, benefiting from the combination of an appropriate training dataset and parameter selection. This notably enhanced computational efficiency when compared to the computationally intensive DFT method aided by GPU acceleration. Validation of the produced interatomic potentials is achieved through Allegro's own evaluation mechanism, yielding exceptional accuracy. Further verification is carried out through LAMMPS molecular dynamics simulations. Structural optimization by energy minimization and NPT Molecular Dynamics simulations are performed for each potential, assessing relaxation processes and energy reduction. Additional structures, including urea, ammonia, uracil, oxalic acid, and acetic acid, are tested, highlighting the potential's versatility in describing systems containing the aforementioned elements. Visualization of the results confirms the scientific accuracy of each structure's relaxation. The findings of this study demonstrate strong scaling and the potential for applications in pharmaceutical research, allowing the exploration of larger molecular structures not previously amenable to computational analysis at this level of accuracy The success of the machine learning approach underscores its potential to revolutionize computational solid-state physics.

Tailoring single-ion magnet properties of coordination polymer C11H18DyN3O9 (Dy-CP) using the radial effective charge model (RECM) and superposition model (SPM).

We investigate Dy-based coordination polymer C11H18DyN3O9 (Dy-CP) exhibiting single-ion magnet (SIM) properties, e.g., quantum tunnelling of magnetization (QTM), magnetic anisotropy, magnetic relaxation, and effective energy barrier (Ueff). To elucidate the underlying mechanisms, crystal field parameters (CFPs) for Dy3+ ions were modelled using the radial effective charge model (RECM) and superposition model (SPM), and the computational packages SIMPRE and SPECTRE. The modelled CFPs enable the prediction of the energy levels and associated wave functions, which successfully explain the field-induced Dy-CP SIM properties. The so-calculated magnetic susceptibility and isothermal magnetization match the experimental data reasonably well. The smaller energy separations of the first (Δ0-1 ∼ 31 cm-1) and the second (Δ0-2 = 74 cm-1) excited Kramers doublets suggest small Ueff = 65 cm-1 for Dy-CP. The magnetic moments of Dy3+ ions exhibit an easy-axis type magnetic anisotropy in the ground state, but change orientation in the excited states due to mixing of states from different Kramers doublets. Low-symmetry CF components play a crucial role in connecting different |±MJ〉 states within the ground multiplet, resulting in QTM and magnetic relaxation to the ground state occurring via the excited states. The RECM and SPM calculated CFP sets are standardized employing the 3DD package to enable meaningful comparison and assessing their mutual equivalence. The results demonstrate the correlation between structural and electronic features of the molecule and site symmetry and distortion of the local coordination polyhedra with SIM properties, offering insights for rational design of new SIMs. The importance of considering low-symmetry aspects in CFP modelling for accurate predictions of magnetic properties is highlighted. This study provides deeper understanding of field-induced behaviour in rare-earth-based SIMs and approaches for rationalization of experimentally measured SIMs' properties.

Electronic energy transfer ionization in naphthalene-CO2 clusters reveals excited states of dry ice.

Electronic energy relaxation and transfer shapes the photochemistry in molecules and materials that are exposed to UV radiation in areas ranging from astrochemistry to biology. The interaction between CO2 and polycyclic aromatic hydrocarbons (PAHs) specifically, is of paramount interest in astrochemically relevant ices, the transition to renewable energy and the development of green chemistry. We investigate the vacuum UV excitation of the naphthalene-CO2 complex and observe excited states of CO2 through a newly identified molecular electronic energy transfer ionization mechanism. We evaluate the spectral development upon cluster growth with time-dependent density functional theory and show that the photoionization spectrum of naphthalene-CO2 closely resembles the photon-stimulated desorption spectrum of CO2 ice. The molecular electronic energy transfer ionization mechanism may affect the energy redistribution and charge balance in the interstellar medium significantly and therefore we discuss its implications for astrochemical models.

Addressing electronic and dynamical evolution of molecules and molecular clusters: DFTB simulations of energy relaxation in polycyclic aromatic hydrocarbons.

We present a review of the capabilities of the density functional based Tight Binding (DFTB) scheme to address the electronic relaxation and dynamical evolution of molecules and molecular clusters following energy deposition via either collision or photoabsorption. The basics and extensions of DFTB for addressing these systems and in particular their electronic states and their dynamical evolution are reviewed. Applications to PAH molecules and clusters, carbonaceous systems of major interest in astrochemical/astrophysical context, are reported. A variety of processes are examined and discussed such as collisional hydrogenation, fast collisional processes and induced electronic and charge dynamics, collision-induced fragmentation, photo-induced fragmentation, relaxation in high electronic states, electronic-to-vibrational energy conversion and statistical versus non-statistical fragmentation. This review illustrates how simulations may help to unravel different relaxation mechanisms depending on various factors such as the system size, specific electronic structure or excitation conditions, in close connection with experiments.

Modeling the Operation of Charge Trap Flash Memory–Part I: The Importance of Carrier Energy Relaxation

Modeling the Operation of Charge Trap Flash Memory–Part I: The Importance of Carrier Energy Relaxation

Local electric field in nanocavities dictates the vibrational relaxation dynamics of interfacial molecules.

Plasmonic nanocavities enable the generation of strong light-matter coupling and exhibit great potential in plasmon-mediated chemical reactions (PMCRs). Although an electric field generated by nanocavities (E n) has recently been reported, its effect on the vibrational energy relaxation (VER) of the molecules in the nanocavities has not been explored. In this study, we reveal the impact of an electric field sensed by molecules (para-substituted thiophenol derivatives) in a nanocavity (E f) on VER processes by employing advanced time-resolved femtosecond sum frequency generation vibrational spectroscopy (SFG-VS) supplemented by electrochemical measurements. The magnitude of E n is almost identical (1.0 ± 0.2 V nm-1) beyond the experimental deviation while E f varies from 0.3 V nm-1 to 1.7 V nm-1 depending on the substituent. An exponential correlation between E f and the complete recovery time of the ground vibrational C[double bond, length as m-dash]C state (T 2) of the phenyl ring is observed. Substances with a smaller T 2 are strongly correlated with the reported macroscopic chemical reactivity. This finding may aid in enriching the current understanding of PMCRs and highlights the possibility of regulating vibrational energy flow into desired reaction coordinates by using a local electric field.

Mechanisms of photoisomerization of the prenylated flavin mononucleotide cofactor: a theoretical study.

The enzymatic decarboxylation of α,β-unsaturated acids using the ferulic acid decarboxylase (Fdc1) enzyme and prenylated flavin mononucleotide (prFMN) cofactor is a potential, environmentally friendly reaction for the biosynthesis of styrene and its derivatives. However, experiments showed that the enzyme activity of Fdc1 depends on the ring structure of prFMN, namely, the iminium and ketimine forms, and the loss of enzyme activity results from prFMNim → prFMNket photoisomerization. To obtain insight into this photochemical process and to improve the enzyme efficiency of Fdc1, two proposed photoisomerization mechanisms with different proton sources for the acid-base reaction were studied herein using theoretical methods. The potential energy surfaces calculated using the density functional theory method with the Becke, 3-parameter, and Lee-Yang-Parr hybrid functionals and DZP basis set (DFT/B3LYP/DZP) and TD-DFT/B3LYP/DZP methods confirmed that the light-dependent reaction occurs in the rate-determining proton transfer process and that the mechanism involving intermolecular proton transfer between prFMNim and Glu282 (external base) is energetically more favorable than that involving intramolecular proton transfer in prFMNim (internal base). The thermodynamic results obtained from the transition state theory method suggested that the exothermic relaxation energy in the photo-to-thermal process can promote the spontaneous formation of a high-energy-barrier transition state, and an effective enzymatic decarboxylation could be achieved by slowing down the formation of the undesirable thermodynamically favorable product (prFMNket). Because the rate constant for formation of the high-energy-barrier transition state varies exponentially over the temperature range of 273-298 K, and experimental results have shown that incubating Fdc1 on ice results in a complete loss of enzyme activity, it is recommended to perform the decarboxylation reaction at 285 K to strike a balance between minimizing enzyme stability loss at 273 K and mitigating the effects of UV irradiation. The computational strategy and fundamental insights obtained in this study could serve as guidelines for future theoretical and experimental investigations on the same and similar photochemical systems.

NATURAL ELECTROMAGNETIC MODES OF A COMPOSITE OPEN STRUCTURE INVOLVING A PERFECTLY CONDUCTING STRIP GRATING, AN INHOMOGENEOUS FERRITE LAYER, AND A MONOLAYER OF GRAPHENE

Subject and Purpose. Сonsidered are the natural modes and their correspondent eigenfrequencies of a composite structure which is nonuniform along one of the coordinates and consists of a lossy ferromagnetic layer placed in a static magnetic field. The layer involves a perfectly conducting strip grating at one of its boundaries and a graphene monolayer at the other. Methods and Methodology. The above stated problem can be approached within the analytical regularization procedure developed for dual series equations. The latter concern a broad class of diffraction problems which include, in particular, the diffraction of monochromatic plane waves on strip gratings placed at the boundary of a gyromagnetic medium. The amplitudes of the electromagnetic eigenmodes can be obtained from the infinite set of homogeneous linear algebraic equations solvable within a truncation technique. The roots of the system’s determinant represent complex-valued eigenfrequencies of the system under investigation. The material parameters adopted in our computations for the ferromagnetic layer correspond to such of yttrium iron garnet. Results. A number of numerical programs have been developed which permit analyzing the dependences of wave field eigenfunctions and complex eigenfrequencies upon geometrical parameters of the structure (such as grating slot width and period, and thickness of the lossy layer), as well as on electrodynamic parameters of the ferromagnet and graphene characteristics, specifically the chemical potential and relaxation energy of electrons. A number of behavioral regularities have been established, as well as the effect of non-uniformity of ferrite layer parameters upon the structure’s eigenfrequencies and wave field eigenfunctions. Conclusions. The structure under study has been shown to be is an open oscillatory system with a set of complex-valued natural frequencies demonstrating finite points of accumulation. The real parts of these eigenfrequencies lie in a certain interval determined by characteristic frequencies of the ferrite layer, while the imaginary parts are negative, such that the correspondent natural modes show an exponential decay with time. The grating edges represent the mirrors which the natural surface oscillations are reflected from, being supported at that by the ferromagnetic medium. The results obtained in this paper can be useful for creating the elemental base for microwave devices and the devices themselves.

High-Temperature Nonequilibrium Air Chemistry from First Principles

We present first-principles calculations for chemically reacting five-species air (N2, N, O2, O, NO) over a range of gas temperatures (T=5000–30,000 K), relying exclusively on ab initio potential energy surfaces (PESs) from the University of Minnesota Computational Chemistry group to describe the forces between atoms. We use these PESs within direct molecular simulations (DMSs) and quasi-classical trajectory (QCT) calculations to determine the coupling of internal energy relaxation to chemical reactions. From DMS we extract the internal energy populations of diatomic species during the quasi-steady-state (QSS) dissociation phase and, for all diatomic species, observe depleted high-energy tails relative to corresponding Boltzmann distributions. A comparison of thermochemical equilibrium rate coefficients (from QCT) with those during QSS (from DMS) helps quantify the macroscopic effects of vibrationally depleted distributions on dissociation. In contrast, Zeldovich exchange reactions are almost unaffected by these vibrationally depleted distributions. Unlike dissociation, they do not exhibit significant vibrational bias and take place at near-thermal rates at all temperatures studied. Furthermore, we quantify the amount of vibrational and rotational energy removed and/or gained in exchange and dissociation reactions. Such macroscopic quantities are of interest for enhancing the fidelity of multitemperature nonequilibrium chemistry models used in computational fluid dynamics codes.

Nonthermal effects in solids after swift heavy ion impact

This contribution is a brief introduction to nonthermal effects related to modifications of the interatomic potential upon ultrafast excitation of the electronic system of solids, primarily focusing on the swift heavy ion track problem. We clarify the difference between the exchange of the kinetic energy of electrons (and holes) scattering on the lattice (electron–phonon coupling, “thermal effects”) and the relaxation of the nonequilibrium potential energy of a solid (“nonthermal effects”). We discuss that at different degrees of electronic excitation, the modification of the interatomic potential may result in various phase transitions without an increase of the atomic temperature, i.e., at room temperature (nonthermal melting, formation of the superionic state), or in atomic acceleration causing “nonthermal heating” of the target atoms. Examples of various theoretically predicted effects are given, supported by known experimental observations.

Investigation of dysprosium oxide substitution on physical, electrical and dielectric properties in sodium borosilicate glass system

Dysprosium oxide doped sodium borosilicate glasses were prepared in this study using a usual melt-quenching process. Further XRD, FTIR, density measurements, electrical conductivity, and dielectric properties were utilized to explore the prepared glassy samples. We found that all produced samples exhibit amorphous nature through X-ray diffraction. Increase in density and molar volume were found when dysprosium oxide concentration increased, which was ascribed to dysprosium oxide's greater molecular weight. Density data was used to calculate and explain several physical characteristics, including rare earth ion concentration (N), polaron radius (rp), internuclear distance (ri), and field strength (F).