Anomalous Energy Minima Studies by Mindo/3

A previous publication¹ utilizing the INDO² and CND0/2³ semi-empirical SCF-MO techniques has shown that these methods predict anomalous minima in the potential surfaces of small molecules and molecular ions, particularly those of type 0-X-0. Two studies have bcmen published concerning the removal of such anomalous pre-dictiors. The first approach⁴ involved reparameterization of the INDO method – specifically involving the Slater exponents α, and the bonding parameters B° of carbon and oxygen – to remove the anomalous iinimum from the potential surface of C0₂. It was de-monstrated that reparameterization could be used to remove the Salse minimum in this case; but only at the expense of the other predictive qualities of INDO, or with the prediction of an unreal-istically broad energy minimum – neither of which could b e con-sidered an acceptable solution.     

Valence band and band gap photoemission study of (1 1 1) In2O3 epitaxial films under interactions with oxygen, water and carbon monoxide

Synchrotron radiation ultraviolet photoemission experiments at photon energies of 150 and 49 eV were performed on an epitaxial layer of (1 1 1) In₂O₃ with good crystallinity as established by a standard scanning probe and diffraction methods. Valence band (VB) and band gap photoemission spectra were monitored under separate oxygen, water and carbon monoxide exposures (100 L) at different activation temperatures within the range utilized for chemiresistive gas sensors (160-450 °C). Large changes in photoemission response within the whole VB were observed for all gases. Regular shifts of the valence band edge relative to the Fermi energy were found under gas exposures on two kinds of surface (partially reduced or partially oxidized), and are interpreted as changes of surface potential. Treatments in oxygen resulted in upward band bending (∼0.5 eV at T = 320 °C). Regardless of activation temperature, treatments in water resulted in downward band bending, but with small changes (<0.1 eV). Reduction properties of carbon monoxide were observed only at high temperatures of T ? 370 °C. At temperatures of 160 and 250 °C unusual “oxidizing” behavior of CO was observed with upward band bending of ∼0.7 eV (160 °C). Oxidizing and reducing effects of the gas interactions with the (1 1 1) In₂O₃ surface in all cases were accompanied by a corresponding behavior, i.e., a decrease or increase in photoemission response from so-called defect states in the band gap near the top of the valence band. The increases of photoemission within a band gap with maxima at binding energies (BE) of 0.4 (O₂-induced peak) and 1.0 eV (CO-induced peak) were, respectively, found for interactions with O₂ and CO for low temperatures (T = 160 and 250 °C). These responses were ascribed to acceptor-like electronic levels of O₂ and CO chemisorption states, respectively. A definite split of the top VB peak (BE ∼ 4.0 eV) was found under CO dosing at 160 °C. Established knowledge of the CO interaction with the (1 1 1) In₂O₃ surface explains earlier revealed acceptor-like behavior of In₂O₃ film conductivity during CO detection at operational temperatures lower than 250 °C through the formation of acceptor-like electronic levels of adsorbed CO molecules.     

The properties and structures of the mono- and the di- vacancy in Cu crystal

The structures and energies of formation and migration of the mono- and di-vacancy in Cu crystal have been described and calculated with modified analytical embedded atom method (MAEAM). The lattice relaxation is considered with molecular dynamics (MD) method at T=0 K. The results show the FN di-vacancy is the most stable and likely occurs in practice from the energy minimization. Compared with the mono-vacancy, the formation energy of the FN di-vacancy is higher than that of a mono-vacancy, but lower than that of two isolated mono-vacancy. The preferred migration mechanism of the FN di-vacancy is multi-jump of either vacancy (rotating the di-vacancy). The calculated migration energy of the FN di-vacancy is lower than that of a mono-vacancy, so the FN di-vacancy is easier to migrate. All of the calculated results are in good agreement with the experimental values.     

Spectral downshifting from blue to near infer red region in Ce3+-Nd3+ co-doped YAG phosphor

The YAG phosphors co-doped with Ce³⁺-Nd³⁺ ions by varying concentration of Nd³⁺ ion from 1 mol% to 15 mol% were successfully synthesized by conventional solid state reaction method. The phosphors were characterized by powder X-ray powder diffraction (XRD) and surface morphology was studied by scanning electronic microscope (SEM). The photoluminescence (PL) properties were studied in near infra red (NIR) and ultra violet visible (UV–VIS) region. The synthesized phosphors can convert a blue region photon (453 nm) into photons of NIR region (1063 nm). The energy transfer (ET) process was studied by time decay curve and PL spectra. The theoretical value of energy transfer efficiency (ETE) was calculated from time decay luminescence measurement and the maximum efficiency approached up to 82.23%. Hence this phosphor could be prime candidate as a downshifting (DS) luminescent convertor (phosphor) in front of crystalline silicon solar cell (c-Si) panels to reduce thermalization loss in the solar cells.     

Reprint of : Thermoelectricity without absorbing energy from the heat sources

We analyze the power output of a quantum dot machine coupled to two electronic reservoirs via thermoelectric contacts, and to two thermal reservoirs – one hot and one cold. This machine is a nanoscale analogue of a conventional thermocouple heat-engine, in which the active region being heated is unavoidably also exchanging heat with its cold environment. Heat exchange between the dot and the thermal reservoirs is treated as a capacitive coupling to electronic fluctuations in localized levels, modeled as two additional quantum dots. The resulting multiple-dot setup is described using a master equation approach. We observe an “exotic” power generation, which remains finite even when the heat absorbed from the thermal reservoirs is zero (in other words the heat coming from the hot reservoir all escapes into the cold environment). This effect can be understood in terms of a non-local effect in which the heat flow from heat source to the cold environment generates power via a mechanism which we refer to as Coulomb heat drag. It relies on the fact that there is no relaxation in the quantum dot system, so electrons within it have a non-thermal energy distribution. More poetically, one can say that we find a spatial separation of the first-law of thermodynamics (heat to work conversion) from the second-law of thermodynamics (generation of entropy). We present circumstances in which this non-thermal system can generate more power than any conventional macroscopic thermocouple (with local thermalization), even when the latter works with Carnot efficiency.     

High pressure X-ray diffraction study of copper hydride at room temperature

Abstract

High pressure X-ray studies on CuH up to 23 GPa have been performed at room temperature using a gasketed diamond anvil cell. The experimental data on the molar volume of CuH as a function of pressure have been fitted to Murnaghan's equation of state giving a bulk modulus: B₀ = 72.5±2 GPa and B₀ = 2.7 ± 0.3. By comparison with the equation of state for pure copper the effective additive volume of hydrogen has been evaluated as a function of pressure. It decreases from 3.2 cm³/mol H, at ambient pressure reaching a flattening value of 1.7cm³hol H at about 60 GPa. This suggests a continuous transition of CuH from ionic or covalent character at normal pressure to metallic hydride behavior at high pressure     

Angle-resolved desorption and removal of surface nitrogen in deNOx

This paper reports on recent progress on angle-resolved desorption leading to structure-sensitive desorption dynamics. The sensitivity is exemplified in NO and N₂O reduction on Pd and Rh surfaces. The energy partitioning in the repulsive desorption of hyper-thermal products into their rotational and translational modes is an indispensable concept to examine the structure of a reaction site from desorbing molecules because it connects the structure of a transition state with each energy of desorbed products. The extent of the energy partitioning will be derived from the desorption-angle dependences of both the rotational and translational energies at each vibrational state. Such energy analysis has never been completed for any thermal reactive desorption. A new type of measurement is thus proposed. Additionally, we discuss the inadequate use of the detailed balance principle in desorption dynamics, which has prevented desorption dynamics from being sensitive to surface structures.     

Remarks on Sharp Interface Limit for an Incompressible Navier-Stokes and Allen-Cahn Coupled System*

The authors are concerned with the sharp interface limit for an incompressible Navier-Stokes and Allen-Cahn coupled system in this paper. When the thickness of the diffuse interfacial zone, which is parameterized by ε, goes to zero, they prove that a solution of the incompressible Navier-Stokes and Allen-Cahn coupled system converges to a solution of a sharp interface model in the L^∞(L²) ∩ L²(H¹) sense on a uniform time interval independent of the smal...     

Molecular adsorption and growth of n-butane adlayers on Pt(1 1 1)

The molecular adsorption of n-butane and the growth of n-butane adlayers on Pt(1 1 1) was investigated using molecular beam techniques, temperature-programmed desorption (TPD) and low-energy electron diffraction (LEED). It is found that as the surface coverage of n-butane increases, structural changes occur in the adlayer at surface temperatures near 98 K that are accompanied by changes in the binding energy and mobility of the adsorbed species. The film growth process can be divided into four distinct coverage regimes. At low coverages (θ<0.14 ML, where 1 ML is defined as one butane molecule per Pt atom) a disordered monolayer forms in which the butane molecules prefer to lie parallel to the surface in order to minimize their binding energy. At coverages from 0.14 to 0.20 ML, ordered regions develop within the monolayer in which the butane molecules also lie parallel to the surface. The binding energy in the ordered phase is lower than that in the disordered phase due to repulsive intermolecular interactions. A more densely-packed ordered phase begins to form at 98 K after the low-coverage ordered phase saturates at 0.20 ML. The experimental results suggest that the n-butane molecules tilt away from the surface in the high-coverage ordered phase. Finally, a disordered second layer phase forms after the high coverage ordered phase saturates at 0.35 ML. The molecules in the second layer are very mobile at 98 K and rapidly diffuse to the edges of the beam spot. Interchange of molecules between the second layer and ordered monolayer is found to govern the net rate of second layer diffusion at surface temperatures less than 133 K. The adsorption probability of n-butane on Pt(1 1 1) continuously increases with increasing coverage, with no significant dependencies on the structure of the n-butane adlayer. This finding indicates that the long-range arrangements and molecular orientations of a mobile alkane adlayer have a negligible influence on the intrinsic adsorption dynamics, suggesting that the energy transfer processes that facilitate adsorption are highly localized.     

Ba2SiO4荧光粉中Ce3+和Eu2+的光谱性质和能量传递

采用高温固相法合成了绿色荧光粉Ba2SiO4:Ce3 ,Eu2 .测量了它们的吸收光谱、激发光谱和发射光谱,观察到了Ba2SiO4中Ce3 对Eu2 发光的敏化现象,发光的敏化作用缘于Ce3 和Eu2 之间的高效无辐射能量传递.