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At least 955 records · Page 53

Spectrally-dependent positive and negative photo-plastic effects in CdZnTe and CdZnTeSe

We studied the Vickers microhardness HV0.025 of CdZnTe and CdZnTeSe samples upon illumination with quasi-monochromatic light with wavelengths ranging between 750 and 1540 nm. We observed that light with a wavelength close to or above the bandgap of the samples results in a positive photo-plastic effect (hardening), and light in the spectral range well below the band gap can lead both to positive or negative effects depending on the parameters of deep levels in the bandgap. We performed measurements of spectrally dependent photoconductivity and compared them with HV0.025. Based on the analysis, we propose a complex qualitative model explaining the spectral dependence of HV0.025 by the charging and neutralization of deep levels by optical transitions between the valence and conduction bands and between the bands and deep levels in the band gap. Tuning of parameters of deep levels could be used to control the sign and magnitude of the photo-plastic effect.

36 MATERIALS SCIENCE↗

Pressure-dependent kinetics of cyclopentene consumption

Recent experiments have uncovered deficiencies in the ability of current kinetic models for cyclopentane combustion to predict species profiles as a function of O2 concentration. One likely source of these discrepancies flows from the limited availability of relevant kinetic data for key functionalized intermediates, requiring the use of distant analogies to estimate their rates. This work fills this gap for cyclopentene, the most prominent C5 intermediate in low-temperature cyclopentane combustion. Ab initio transition-state-theory based master equation methods are used to calculate pressure-dependent rate constants across four potential energy surfaces (C5H8 + OH, C5H8 + HO2, C5H7, and C5H7 + O2). Potential energy surfaces are characterized at the CCSD(T)-F12/cc-pVDZ-F12//revDSD-PBEP86-D3BJ/def2-TZVPP level of theory. Pressure-dependent rate constants and branching fractions are determined via 1D master equation calculations. The results are used to analyze the competition for radicals between cyclopentene and cyclopentane in the intermediate temperature region, and to identify the dominant pathways flowing from these initiation channels. On the OH initiation surface, we find good agreement with recently published experimental rate constants at high temperature, and we elucidate the complex temperature dependence below 800 K, where 𝜋𝜋 addition becomes prominent. On the HO2 initiation surface, we find an interesting alternative route to bicyclic ether formation via well-skipping over the HO2 adduct well. On the cyclopentenyl radical surface, the major product is cyclopentadiene plus H. On the cyclopentenyl + O2 surface, we find that resonance stabilization largely prevents the allylic radical from undergoing oxidation, whereas the alkylic radical has a somewhat elevated propensity for oxidation pathways relative to cyclopentyl.

ab initio calculations↗

Subneurotoxic copper(II)-induced NF-κB-dependent microglial activation is associated with mitochondrial ROS

Microglia-mediated neuroinflammation and the associated neuronal damage play critical roles in the pathogenesis of neurodegenerative disorders. Evidence shows an elevated concentration of extracellular copper(II) in the brains of these disorders, which may contribute to neuronal death through direct neurotoxicity. Here we explored whether extracellular copper(II) triggers microglial activation. Primary rat microglia and murine microglial cell line BV-2 cells were cultured and treated with copper(II). The content of tumor necrosis factor-α (TNF-α) and nitric oxide in the medium was determined. Extracellular hydrogen peroxide was quantified by a fluorometric assay with Amplex Red. Mitochondrial superoxide was measured by MitoSOX oxidation. At subneurotoxic concentrations, copper(II) treatment induced a dose- and time-dependent release of TNF-α and nitric oxide from microglial cells, and caused an indirect, microglia-mediated neurotoxicity that was blocked by inhibition of TNF-α and nitric oxide production. Copper(II)-initiated microglial activation was accompanied with reduced IkB-α expression as well as phosphorylation and translocation of nuclear factor-κB (NF-κB) p65 and was blocked by NF-κB inhibitors (BAY11-7082 and SC-514). Moreover, copper(II) treatment evoked a rapid release of hydrogen peroxide from microglial cells, an effect that was not affected by NADPH oxidase inhibitors. N-acetyl-cysteine, a scavenger of reactive oxygen species (ROS), abrogated copper(II)-elicited microglial release of TNF-α and nitric oxide and subsequent neurotoxicity. Importantly, mitochondrial production of superoxide, paralleled to extracellular release of hydrogen peroxide, was induced after copper(II) stimulation. Our findings suggest that extracellular copper(II) at subneurotoxic concentrations could trigger NF-κB-dependent microglial activation and subsequent neurotoxicity. NADPH oxidase-independent, mitochondria-derived ROS may be involved in this activation. - Highlights: • Subneurotoxic copper(II) triggers NF-κB-dependent microglial activation. • This activation leads to hippocampal neuronal death. • This activation may involve mitochondria-derived reactive oxygen species.

60 APPLIED LIFE SCIENCES↗

Bisphenol A impairs the memory function and glutamatergic homeostasis in a sex-dependent manner in mice: Beneficial effects of diphenyl diselenide

Bisphenol A (BPA) is a compound integrated in commodities, which consequently increases the human exposure to this toxicant. The deleterious effects of BPA exposure during periods of brain development have been documented mainly concerning the impairment in memory functions. Diphenyl diselenide (PhSe){sub 2}, an organoselenium compound, shows protective/restorative effects against memory deficits in experimental models. Thus, this study investigated the effects of (PhSe){sub 2} on the memory impairments induced by BPA exposure to male and female mice and the possible involvement of glutamatergic system in these effects. Three-week-old male and female Swiss mice received BPA (5 mg/kg), intragastrically, from 21st to 60th postnatal day. After, the animals were intragastrically treated with (PhSe){sub 2} (1 mg/kg) during seven days. The mice performed the behavioral memory tests and the [{sup 3}H] glutamate uptake and NMDA receptor subunits (2A and 2B) analyses were carried out in the hippocampus and cerebral cortex of mice. The results demonstrated that the BPA exposure induced impairment of object recognition memory in both sexes. However, it caused impairments in spatial memory in female and in the passive avoidance memory in male mice. Besides, BPA caused a decrease in the [{sup 3}H] glutamate uptake and NMDA receptor subunit levels in the cortical and hippocampal regions depending on the sex. Treatment with (PhSe){sub 2} reversed in a sex-independent manner the behavioral impairments and molecular alterations. In conclusion, BPA had a negative effect in different memory types as well as in the glutamatergic parameters in a sex-dependent manner and (PhSe){sub 2} treatment was effective against these alterations. - Highlights: • BPA exposure induced memory impairment in a sex dependent manner in mice. • (PhSe){sub 2} reversed memory impairments caused by BPA exposure in mice. • (PhSe){sub 2} modulated hippocampal and cortical [{sup 3}H]glutamate uptake in mice. • (PhSe){sub 2} restored the hippocampal and cortical NMDA receptor subunits levels.

60 APPLIED LIFE SCIENCES↗

The Temperature Dependence of the Langmuir Adsorption Model for a Single-Site Metal–Organic Framework

The single-site Langmuir adsorption model, also known as the Langmuir isotherm equation, is one of the simplest possible descriptions of adsorption phenomena, and yet finds widespread applicability across a range of disciplines. In its simplest form, it is deployed to treat adsorption equilibria at constant temperature (i.e., along isotherms); however, at the heart of its derivation is a more general class of models that each incorporate an explicit temperature dependence, subject to assumptions about the spatial/translational degrees of freedom of the adsorbed species. In this work, measurements of the temperature dependence of supercritical adsorption of H 2 on a single-site metal-organic framework (MOF) are presented, and fitted using a range of Langmuir models with distinct treatments of degrees of freedom in the adsorbed phase. Surprisingly, all of the models can be used to adequately represent the measured data, despite yielding significantly different values for binding energy and the temperature dependence of the isosteric enthalpy of adsorption (i.e., the isosteric heat, qst). Furthermore, a critical finding is that the mean-temperature isosteric enthalpy of adsorption remains consistent across all models within experimental error, highlighting its reliability for evaluating adsorption thermodynamics.

08 HYDROGEN↗

Inverse Temperature Dependence of Charge Carrier Hopping in Quantum Dot Solids

In semiconductors, increasing mobility with decreasing temperature is a signature of charge carrier transport through delocalized bands. We show that this behavior can also occur in nanocrystal solids due to temperature-dependent structural transformations. Using a combination of broadband infrared transient absorption spectroscopy and numerical modeling, we investigate the temperature-dependent charge transport properties of well-ordered PbS quantum dot (QD) solids. Contrary to expectations, we observe that the QD-to-QD charge tunneling rate increases with decreasing temperature, while simultaneously exhibiting thermally activated nearest-neighbor hopping behavior. Using synchrotron grazing-incidence small-angle X-ray scattering, we show that this trend is driven by a temperature-dependent reduction in nearest-neighbor separation that is quantitatively consistent with the measured tunneling rate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Frequency dependence of electron dynamics during femtosecond laser resonant photoionization of Li{sub 4} cluster

This study investigates the resonant effects on nonlinear photoionization of Li{sub 4} cluster under femtosecond laser irradiation. The real-time and real-space time-dependent density functional theory is applied to describe the optical linear response and nonlinear electron dynamics during the laser-material interactions. The calculations describe well the behaviors of the ionization process for both the off resonance and on resonance cases. For given laser intensities, the frequency dependence of electron ionization and energy absorption on multiphoton and/or tunnel ionization mechanisms is investigated. Theoretical results show that (1) the off resonance behaves as a classical oscillator whereas resonance leads to an internal excitation with subsequent emission of electrons after the laser termination; (2) when multiphoton ionization dominates, the frequency dependence of emitted electrons and absorbed energy coincides with trend of the spectral cross section for photon absorption; (3) while when tunnel ionization becomes significant, the aforementioned correlation gradually disappears, and the enhancement of resonant effect on photoionization is not manifest.

36 MATERIALS SCIENCE↗

Temperature dependent junction capacitance-voltage characteristics of Ni embedded TiN/SiO{sub 2}/p-Si metal–insulator–semiconductor structure

This work presents the junction capacitance–voltage characteristics of highly textured/epitaxial Ni nanoparticle embedded in TiN matrix (TiN(Ni)) metal-insulator-semiconductor TiN(Ni)/SiO{sub 2}/p-Si (100) heterojunction in the temperature range of 10–300 K. This heterojunction behaves as metal-semiconductor junction with unavoidable leakage through native oxide SiO{sub 2} layer. The clockwise hysteresis loop has been observed in the capacitance-voltage characteristics measured at various frequencies mainly due to presence of trap centers at the TiN(Ni)/SiO{sub 2} interface and these are temperature dependent. The spin-dependent trap charge effect at the interface influences the quadratic nature of the capacitance with magnetic field. The junction magnetocapacitance (JMC) is observed to be dependent on both temperature and frequency. The highest JMC of this heterojunction has been observed at 200 K at higher frequencies (100 kHz–1 MHz). It is found that there is not much effect of band structure modification under magnetic field causing the JMC.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effect of annealing on the temperature dependence of inelastic tunneling contributions vis-à-vis tunneling magnetoresistance and barrier parameters in CoFe/MgO/NiFe magnetic tunnel junctions

The effect of annealing on the changes in the inelastic tunneling contributions in tunneling conductance of ion beam sputtered CoFe/MgO/NiFe magnetic tunnel junctions (MTJs) is investigated. The inelastic contributions are evaluated using hopping conduction model of Glazman and Matveev in the temperature range of 25–300 K. The hopping through number of series of localized states present in the barrier due to structural defects increases from 9 (in as deposited MTJ) to 18 after annealing (at 200 °C/1 h); although no changes in the interface roughness of CoFe-MgO and MgO-NiFe interfaces are observed as revealed by the x-ray reflectance studies on planar MTJs. The bias dependence of tunneling magnetoresistance (TMR) at 25 K is found to get improved after annealing as revealed by the value V{sub 1/2} (the bias value at which the TMR reaches to half of its value at nearly zero bias); which is 78 mV (in MTJ annealed at 200 °C/1 h) 2.5 times the value of 33 mV (in as deposited MTJ). At 25 K the inelastic tunneling spectra revealed the presence of zero bias anomaly and magnon excitations in the range of 10–15 mV. While the barrier height exhibited a strong temperature dependence with nearly 100% increase from the value at 300 K to 25 K, the temperature dependence of TMR becomes steep after annealing.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Frequency-dependent quantum capacitance and plasma wave in monolayer transition metal dichalcogenides

Frequency-dependent quantum capacitance C{sub Q} of monolayer transition metal dichalcogenides (TMDs) is computed and compared to that of graphene. It is found that the frequency dependence of C{sub Q} in TMDs differs drastically from that of graphene which has a divergent point. The plasma resonance forms when the quantum capacitance is negative and has the same magnitude as the electrostatic capacitance. The calculation shows that the plasma in TMDs depends on the band-structure-limited velocity, band gap, and doping density, which can be controlled via gate biases. The plasma frequencies of TMDs are in the rage of terahertz useful for various applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Spin-dependent transport behavior in C{sub 60} and Alq{sub 3} based spin valves with a magnetite electrode (invited)

The spin-dependent transport behavior in organic semiconductors (OSs) is generally observed at low temperatures, which likely results from poor spin injection efficiency at room temperature from the ferromagnetic metal electrodes to the OS layer. Possible reasons for this are the low Curie temperature and/or the small spin polarization efficiency for the ferromagnetic electrodes used in these devices. Magnetite has potential as an advanced candidate for use as the electrode in spintronic devices, because it can achieve 100% spin polarization efficiency in theory, and has a high Curie temperature (850 K). Here, we fabricated two types of organic spin valves using magnetite as a high efficiency electrode. C{sub 60} and 8-hydroxyquinoline aluminum (Alq{sub 3}) were employed as the OS layers. Magnetoresistance ratios of around 8% and over 6% were obtained in C{sub 60} and Alq{sub 3}-based spin valves at room temperature, respectively, which are two of the highest magnetoresistance ratios in organic spin valves reported thus far. The magnetoresistance effect was systemically investigated by varying the thickness of the Alq{sub 3} layer. Moreover, the temperature dependence of the magnetoresistance ratios for C{sub 60} and Alq{sub 3}-based spin valves were evaluated to gain insight into the spin-dependent transport behavior. This study provides a useful method in designing organic spin devices operated at room temperature.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Sequence-dependent theory of oligonucleotide hybridization kinetics

A theoretical approach to the prediction of the sequence and temperature-dependent rate constants for oligonucleotide hybridization reactions has been developed based on the theory of relaxation kinetics. One-sided and two-sided melting reaction mechanisms for oligonucleotide hybridization reactions have been considered, analyzed, modified, and compared to select a physically consistent as well as robust model for prediction of the relaxation times of DNA hybridization reactions that agrees with the experimental evidence. The temperature- and sequence-dependent parameters of the proposed model have been estimated using available experimental data. The relaxation time model that we developed has been combined with the nearest neighbor model of hybridization thermodynamics to estimate the temperature- and sequence-dependent rate constants of an oligonucleotide hybridization reaction. The model-predicted rate constants are compared to experimentally determined rate constants for the same oligonucleotide hybridization reactions. Finally, we consider a few important applications of kinetically controlled DNA hybridization reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of Gaussian white noise on the frequency-dependent first nonlinear polarizability of doped quantum dot

We investigate the profiles of diagonal components of frequency-dependent first nonlinear (β{sub xxx} and β{sub yyy}) optical response of repulsive impurity doped quantum dots. We have assumed a Gaussian function to represent the dopant impurity potential. This study primarily addresses the role of noise on the polarizability components. We have invoked Gaussian white noise consisting of additive and multiplicative characteristics (in Stratonovich sense). The doped system has been subjected to an oscillating electric field of given intensity, and the frequency-dependent first nonlinear polarizabilities are computed. The noise characteristics are manifested in an interesting way in the nonlinear polarizability components. In case of additive noise, the noise strength remains practically ineffective in influencing the optical responses. The situation completely changes with the replacement of additive noise by its multiplicative analog. The replacement enhances the nonlinear optical response dramatically and also causes their maximization at some typical value of noise strength that depends on oscillation frequency.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Characterization of multielectron dynamics in molecules: A multiconfiguration time-dependent Hartree-Fock picture

Using the framework of multiconfiguration theory, where the wavefunction Φ(t) of a many-electron system at time t is expanded as Φ(t)=∑{sub I}C{sub I}(t)Φ{sub I}(t) in terms of electron configurations (Φ{sub I}(t)), we divided the total electronic energy E(t) as E(t)=∑{sub I}|C{sub I}(t)|{sup 2}E{sub I}(t) . Here E{sub I}(t) is the instantaneous phase changes of C{sub I}(t) regarded as a configurational energy associated with Φ{sub I}(t). We then newly defined two types of time-dependent states: (i) a state at which the rates of population transfer among configurations are all zero; (ii) a state at which (E{sub I}(t)) associated with the quantum phases of C{sub I}(t) are all the same. We call the former time-dependent state a classical stationary state by analogy with the stationary (steady) states of classical reaction rate equations and the latter one a quantum stationary state. The conditions (i) and (ii) are satisfied simultaneously for the conventional stationary state in quantum mechanics. We numerically found for a LiH molecule interacting with a near-infrared (IR) field ε(t) that the condition (i) is satisfied whenever the average velocity of electrons is zero and the condition (ii) is satisfied whenever the average acceleration is zero. We also derived the chemical potentials μ{sub j}(t) for time-dependent natural orbitals ϕ{sub j}(t) of a many-electron system. The analysis of the electron dynamics of LiH indicated that the temporal change in Δμ{sub j}(t) ≡ μ{sub j}(t) + ε(t) · d{sub j}(t) − μ{sub j}(0) correlates with the motion of the dipole moment of ϕ{sub j}(t), d{sub j}(t). The values Δμ{sub j}(t) are much larger than the energy ζ{sub j}(t) directly supplied to ϕ{sub j}(t) by the field, suggesting that valence electrons exchange energy with inner shell electrons. For H{sub 2} in an intense near-IR field, the ionization efficiency of ϕ{sub j}(t) is correlated with Δμ{sub j}(t). Comparing Δμ{sub j}(t) to ζ{sub j}(t), we found that energy accepting orbitals of Δμ{sub j}(t) > ζ{sub j}(t) indicate high ionization efficiency. The difference between Δμ{sub j}(t) and ζ{sub j}(t) is significantly affected by electron-electron interactions in real time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Growth-temperature dependence of optical spin-injection dynamics in self-assembled InGaAs quantum dots

The growth-temperature dependence of the optical spin-injection dynamics in self-assembled quantum dots (QDs) of In{sub 0.5}Ga{sub 0.5}As was studied by increasing the sheet density of the dots from 2 × 10{sup 10} to 7 × 10{sup 10} cm{sup −2} and reducing their size through a decrease in growth temperature from 500 to 470 °C. The circularly polarized transient photoluminescence (PL) of the resulting QD ensembles was analyzed after optical excitation of spin-polarized carriers in GaAs barriers by using rate equations that take into account spin-injection dynamics such as spin-injection time, spin relaxation during injection, spin-dependent state-filling, and subsequent spin relaxation. The excitation-power dependence of the transient circular polarization of PL in the QDs, which is sensitive to the state-filling effect, was also examined. It was found that a systematic increase occurs in the degree of circular polarization of PL with decreasing growth temperature, which reflects the transient polarization of exciton spin after spin injection. This is attributed to strong suppression of the filling effect for the majority-spin states as the dot-density of the QDs increases.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Composition dependent valence band order in c-oriented wurtzite AlGaN layers

The valence band order of polar wurtzite aluminum gallium nitride (AlGaN) layers is analyzed for a dense series of samples, grown heteroepitaxially on sapphire substrates, covering the complete composition range. The excitonic transition energies, found by temperature dependent photoluminescence (PL) spectroscopy, were corrected to the unstrained state using input from X-ray diffraction. k∙p theory yields a critical relative aluminum concentration x{sub c}=(0.09±0.05) for the crossing of the uppermost two valence bands for strain free material, shifting to higher values for compressively strained samples, as supported by polarization dependent PL. The analysis of the strain dependent valence band crossing reconciles the findings of other research groups, where sample strain was neglected. We found a bowing for the energy band gap to the valence band with Γ₉ symmetry of b{sub Γ₉}=0.85eV, and propose a possible bowing for the crystal field energy of b{sub cf}=-0.12eV. A comparison of the light extraction efficiency perpendicular and parallel to the c axis of Al{sub x}Ga{sub 1-x}N/Al{sub y}Ga{sub 1-y}N quantum well structures is discussed for different compositions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Temperature-dependent templated growth of porphine thin films on the (111) facets of copper and silver

The templated growth of the basic porphyrin unit, free-base porphine (2H-P), is characterized by means of X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy measurements and density functional theory (DFT). The DFT simulations allow the deconvolution of the complex XPS and NEXAFS signatures into contributions originating from five inequivalent carbon atoms, which can be grouped into C–N and C–C bonded species. Polarization-dependent NEXAFS measurements reveal an intriguing organizational behavior: On both Cu(111) and Ag(111), for coverages up to one monolayer, the molecules adsorb undeformed and parallel to the respective metal surface. Upon increasing the coverage, however, the orientation of the molecules in the thin films depends on the growth conditions. Multilayers deposited at low temperatures exhibit a similar average tilting angle (30° relative to the surface plane) on both substrates. Conversely, for multilayers grown at room temperature a markedly different scenario exists. On Cu(111) the film thickness is self-limited to a coverage of approximately two layers, while on Ag(111) multilayers can be grown easily and, in contrast to the bulk 2H-P crystal, the molecules are oriented perpendicular to the surface. This difference in molecular orientation results in a modified line-shape of the C 1s XPS signatures, which depends on the incident photon energy and is explained by comparison with depth-resolved DFT calculations. Simulations of ionization energies for differently stacked molecules show no indication for a packing-induced modification of the multilayer XP spectra, thus indicating that the comparison of single molecule calculations to multilayer data is justified.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of reagent rotational excitation on the H + CHD{sub 3} → H{sub 2} + CD{sub 3} reaction: A seven dimensional time-dependent wave packet study

Seven-dimensional time-dependent wave packet calculations have been carried out for the title reaction to obtain reaction probabilities and cross sections for CHD{sub 3} in J{sub 0} = 1, 2 rotationally excited initial states with k{sub 0} = 0 − J{sub 0} (the projection of CHD{sub 3} rotational angular momentum on its C{sub 3} axis). Under the centrifugal sudden (CS) approximation, the initial states with the projection of the total angular momentum on the body fixed axis (K{sub 0}) equal to k{sub 0} are found to be much more reactive, indicating strong dependence of reactivity on the orientation of the reagent CHD{sub 3} with respect to the relative velocity between the reagents H and CHD{sub 3}. However, at the coupled-channel (CC) level this dependence becomes much weak although in general the K{sub 0} specified cross sections for the K{sub 0} = k{sub 0} initial states remain primary to the overall cross sections, implying the Coriolis coupling is important to the dynamics of the reaction. The calculated CS and CC integral cross sections obtained after K{sub 0} averaging for the J{sub 0} = 1, 2 initial states with all different k{sub 0} are essentially identical to the corresponding CS and CC results for the J{sub 0} = 0 initial state, meaning that the initial rotational excitation of CHD{sub 3} up to J{sub 0} = 2, regardless of its initial k{sub 0}, does not have any effect on the total cross sections for the title reaction, and the errors introduced by the CS approximation on integral cross sections for the rotationally excited J{sub 0} = 1, 2 initial states are the same as those for the J{sub 0} = 0 initial state.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗