Ab initio potential energy surface and anharmonic vibration spectrum of NF_(3)^(+)

Potential energy surfaces(PESs), vibrational frequencies, and infrared spectra are calculated for NF_(3)^(+) using ab initio calculations, based on UCCSD(T)/cc-p VTZ combined with vibrational configuration interaction(VCI). Based on an iterative algorithm, the surfaces(SURF) program adds automatic points to the lattice representation of the potential function, the one-dimensional and two-dimensional PESs are calculated after reaching a convergence threshold, finally the smooth image of the potential energy surface is fitted. The PESs accurately account for the interaction between the different modes, with the mode q_(6) symmetrical stretching vibrations having the greatest effect on the potential energy change of the whole system throughout the potential energy surface shift. The anharmonic frequencies are obtained when the VCI matrix is diagonalized. Fundamental frequencies, overtones, and combination bands of NF_(3)^(+) are calculated, which generate the degenerate phenomenon between their frequencies. Finally, the calculated anharmonic frequency is used to plot the infrared spectra.Modal antisymmetric stretching ν_(5) and symmetric stretching ν_(6) exhibit a phenomenon of large-intensity borrowing. This study can provide data to support the characterization in the laboratory.

Impact of Initial Soil Conditions on Soil Hydrothermal and Surface Energy Fluxes in the Permafrost Region of the Tibetan Plateau

Accurate initial soil conditions play a crucial role in simulating soil hydrothermal and surface energy fluxes in land surface process modeling.This study emphasized the influence of the initial soil temperature(ST)and soil moisture(SM)conditions on a land surface energy and water simulation in the permafrost region in the Tibetan Plateau(TP)using the Community Land Model version 5.0(CLM5.0).The results indicate that the default initial schemes for ST and SM in CLM5.0 were simplistic,and inaccurately represented the soil characteristics of permafrost in the TP which led to underestimating ST during the freezing period while overestimating ST and underestimating SLW during the thawing period at the XDT site.Applying the long-term spin-up method to obtain initial soil conditions has only led to limited improvement in simulating soil hydrothermal and surface energy fluxes.The modified initial soil schemes proposed in this study comprehensively incorporate the characteristics of permafrost,which coexists with soil liquid water(SLW),and soil ice(SI)when the ST is below freezing temperature,effectively enhancing the accuracy of the simulated soil hydrothermal and surface energy fluxes.Consequently,the modified initial soil schemes greatly improved upon the results achieved through the long-term spin-up method.Three modified initial soil schemes experiments resulted in a 64%,88%,and 77%reduction in the average mean bias error(MBE)of ST,and a 13%,21%,and 19%reduction in the average root-mean-square error(RMSE)of SLW compared to the default simulation results.Also,the average MBE of net radiation was reduced by 7%,22%,and 21%.

Nonlinear change of ion-induced secondary electron emission in theκ-Al_(2)O_(3) surface charging from first-principle modelling

Secondary electron emission(SEE)induced by the positive ion is an essential physical process to influence the dynamics of gas discharge which relies on the specific surface material.Surface charging has a significant impact on the material properties,thereby affecting the SEE in the plasma-surface interactions.However,it does not attract enough attention in the previous studies.In this paper,SEE dependent on the charged surface of specific materials is described with the computational method combining a density functional theory(DFT)model from the first-principle theory and the theory of Auger neutralization.The effect ofκ-Al2O3 surface charge,as an example,on the ion-induced secondary electron emission coefficient(SEEC)is investigated by analyzing the defect energy level and band structure on the charged surface.Simulation results indicate that,with the surface charge from negative to positive,the SEEC of a part of low ionization energy ions(such as Ei=12.6 eV)increases first and then decreases,exhibiting a nonlinear changing trend.This is quite different from the monotonic decreasing tendency observed in the previous model which simplifies the electronic structure.This irregular increase of the SEEC can be attributed to the lower escaped probability of orbital energy.The results further illustrate that the excessive charge could cause the bottom of the conduction band close to the valence band,thus leading to the decrease of the orbital energy occupied by the excited electrons.The nonlinear change of SEEC demonstrates a more realistic situation of how the electronic structure of material surface influences the SEE process.This work provides an accurate method of calculating SEEC from specific materials,which is urgent in widespread physical scenarios sensitive to surface materials,such as increasingly growing practical applications concerning plasma-surface interactions.

Surface deterioration dependent on the crystal facets of spinel LiNi_(0.5)Mn_(1.5)O_(4) cathode active material

The spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)cathode active materials(CAMs)are considered a promising alternative to commercially available cathodes such as layered and polyanion oxide cathodes,primarily due to their notable safety and high energy density,particularly in their single-crystal type.Nevertheless,the industrial application of the LNMO CAMs is severely inhibited due to the interfacial deterioration and corrosion under proton-rich and high-voltage conditions.This study successfully designed and synthesized two typical types of crystal facets-exposed single-crystal LNMO CAMs.By tracking the electrochemical deterioration and chemical corrosion evolution,this study elucidates the surface degradation mechanisms and intrinsic instability of the LNMO,contingent upon their crystal facets.The(111)facet,due to its elevated surface energy,is found to be more susceptible to external attack compared to the(100)and(110)facets.Our study highlights the electrochemical corrosion stability of crystal plane engineering for spinel LNMO CAMs.

Enhanced energy-absorbing and sound-absorbing capability of functionally graded and helicoidal lattice structures with triply periodic minimal surfaces

Lattice structures have drawn much attention in engineering applications due to their lightweight and multi-functional properties.In this work,a mathematical design approach for functionally graded(FG)and helicoidal lattice structures with triply periodic minimal surfaces is proposed.Four types of lattice structures including uniform,helicoidal,FG,and combined FG and helicoidal are fabricated by the additive manufacturing technology.The deformation behaviors,mechanical properties,energy absorption,and acoustic properties of lattice samples are thoroughly investigated.The load-bearing capability of helicoidal lattice samples is gradually improved in the plateau stage,leading to the plateau stress and total energy absorption improved by over 26.9%and 21.2%compared to the uniform sample,respectively.This phenomenon was attributed to the helicoidal design reduces the gap in unit cells and enhances fracture resistance.For acoustic properties,the design of helicoidal reduces the resonance frequency and improves the peak of absorption coefficient,while the FG design mainly influences the peak of absorption coefficient.Across broad range of frequency from 1000 to 6300 Hz,the maximum value of absorption coefficient is improved by18.6%-30%,and the number of points higher than 0.6 increased by 55.2%-61.7%by combining the FG and helicoidal designs.This study provides a novel strategy to simultaneously improve energy absorption and sound absorption properties by controlling the internal architecture of lattice structures.

Effects of laser energy on the surface quality and properties of electrodeposited zinc-nickel-molybdenum coatings

As a substitute for toxic cadmium coatings in the aerospace industry,zinc-nickel coatings have excellent application prospects,and their properties can be improved by adding molybdenum.In this study,laser-assisted electrodeposition is used to improve the surface quality and properties of Zn–Ni–Mo coatings,with investigation of how laser energy in the range of 0–21.1μJ affects their element content,surface morphology,crystal phase,microhardness,residual internal stress,and corrosion resistance.The laser irradiation accelerates the electrodeposition,refines the grain size,improves the hydrogen adsorption,and reduces the residual tensile stress,and a laser energy of 15.4μJ gives the highest Ni and Mo contents and the lowest Zn content,as well as the optimum surface morphology,microhardness,residual internal stress,and corrosion resistance of the coating.

Stereodynamics Study of Li+HF→LiF+H Reactions on X^2A’ Potential Energy Surface at Collision Energies below 5.00 kcal/mol

The product rotational polarizations of reaction Li-SHF→LiF-kH at different collision energies, as well as at the different vibrational states and rotational states, are calculated by using the quasi-classical trajectory method based on a new potential energy surface constructed by Aguado et al. [J. Chem. Phys. 119（2003） 10088]. We investigate the Mignment and the orientation of the product molecule by calculating the P（θr, φr） distribu- tions describing polar angle distribution, the P（θr） distributions describing the k-j＇ correlation and the P（φr） distributions describing the k-k＇-j＇ correlation. We also explore the dependence of reaction probabilities and cross sections on the rotational and vibrational quantum number of the title reaction. It is concluded that the vibrational state has more important impact on the angular distribution, reaction probability and cross section.

Mineral cleavage nature and surface energy: Anisotropic surface broken bonds consideration

The population of surface broken bonds of some typical sulfide, oxide and salt-type minerals which may belong to cubic, tetragonal, hexagonal, or orthorhombic system, were calculated. In terms of the calculation results, the cleavage natures of these minerals were analyzed, and the relationship between surface broken bonds density and surface energy was also established. The results show that the surface broken bonds properties could be used to predict the cleavage nature of most of minerals, and the predicted cleavage planes agree well with those reported in previous literature. Moreover, this work explored a rule that, surface broken bonds density is directly related to surface energy with determination coefficient（R2） of over 0.8, indicating that the former is a dominant factor to determine the latter. Therefore, anisotropic surface broken bonds density can be used to predict the stability of mineral surface and the reactivity of surface atoms.

Surface energies and appearances of commonly exposed surfaces of scheelite crystal

Surface energies of five different surfaces of scheelite crystal were calculated using density functional theory （DFT）. Based on the calculation results, the predominantly exposed surfaces in the morphologies of scheelite crystals were predicted. {112} and {001} cleavage surfaces and {112} crystal surface are the commonly exposed surfaces, which are consistent with both previous literatures and the present experimental observations based on the XRD. Cleavage generates more easily along {112} surfaces than along {001} surfaces due to their different interlayer spacings. The surface roughness and appearance of different predominantly exposed surfaces were then investigated using AFM. The roughness of smooth {112} cleavage surface is the lowest among these three surfaces. On {001} cleavage surface, terraces are flat and separated by steps of about 10 nm in height. Subsequently, contact angle measurements were adopted to evaluate the wettability and surface energies of these surfaces. The surface energies evaluated directly correspond to the trend calculated with DFT.

Novel method for exactly evaluating the energy of Catmull-Clark subdivision surfaces

A novel method is produced to evaluate the energy of the Catmull-Clark subdivision surface including extraordinary points in the control mesh. A closed-form analytic formula for thin plate energy of the Catmull-Clark subdivision surface of arbitrary topology is derived through translating the Catmull-Clark subdivision surface into bi-cubic B-spline surface pieces. Using this method, both the membrane energy and the thin plate energy can be evaluated without requiring recursive subdivision. Therefore, it is more efficient and more accurate than the existing methods for calculating the energy of the Catmull-Clark subdivision surface with arbitrary topology. The example of surface fairing demonstrates that this method is efficient and successful for evaluating the energy of subdivision surfaces.

Global Potential Energy Surface for the H＋CH4←→H2＋CH3 Reaction using Neural Networks

A globla potential energy surface （PES） for the H＋CH4←→H2＋CH3 reaction has been constructed using the neural networks method based on 47783 high level ab initio geometry points. Extensive quasi-classical trajectories and quantum scattering calculations were carried out to check the convergence of the PES. This PES, fully converged with respect to the fitting procedure and the number of ab initio points, has a very small fitting error, and is much faster on evaluation than the modified Shepard interpolating PES, representing the best available PES for this benchmark polyatomic system.

Theoretical Study on Dissociation Potential Energy Surface of Peroxynitric Acid

The lowest energy structures of peroxynitric acid have been studied with B3LYP/6-311＋ G（2d,2p） method. The potential energy surfaces （PES） along the O-N and O-O bonds have been scanned at CCSD（T）/aug-cc-pVDZ level, respectively. The calculated results show that on the O-N PES, the O3-N4 bond length of the loose transition state is 2.82A^° and the corresponding energy barrier is 25.6 kcal/mol, while on the O-O PES, the loose transition state with of O2-O3 bond length of 2.35A^° has the energy barrier of 37.4 kcal/mol. Thus the primary reaction path for peroxynitric acid is the dissociation into HO2 and NO2.

Effect of Surface Potential Barrier on the Electron Energy Distribution of NEA Photocathodes

By calculating the energy distribution of electrons reaching the photocathode surface and solving the Schrodinger equation that describes the behavior of an electron tunneling through the surface potential barrier,we obtain an equation to calculate the emitted electron energy distribution of transmission-mode NEA GaAs photocathodes. Accord- ing to the equation,we study the effect of cathode surface potential barrier on the electron energy distribution and find a significant effect of the barrier-Ⅰ thickness or end height,especially the thickness,on the quantum efficiency of the cath- ode. Barrier Ⅱ has an effect on the electron energy spread, and an increase in the vacuum level will lead to a narrower electron energy spread while sacrificing a certain amount of cathode quantum efficiency. The equation is also used to fit the measured electron energy distribution curve of the transmission-mode cathode and the parameters of the surface barri- er are obtained from the fitting. The theoretical curve is in good agreement with the experimental curve.

A Global ab initio Potential Energy Surface for F+H_(2)→HF+H

A global three dimensional potential energy surface for the F＋H2→HF＋H reaction has been developed by spline interpolation of about 15,000 symmetry-unique ab initio points, obtained from the multi-reference configuration interaction level with Davidson correction using the aug-cc-pV5Z basis set. In the entrance channel the spin-orbit coupling energy is also included.

Influence of Surface Types on the Seasonality and Inter-Model Spread of Arctic Amplification in CMIP6

A robust phenomenon termed the Arctic Amplification(AA)refers to the stronger warming taking place over the Arctic compared to the global mean.The AA can be confirmed through observations and reproduced in climate model simulations and shows significant seasonality and inter-model spread.This study focuses on the influence of surface type on the seasonality of AA and its inter-model spread by dividing the Arctic region into four surface types:ice-covered,ice-retreat,ice-free,and land.The magnitude and inter-model spread of Arctic surface warming are calculated from the difference between the abrupt-4×CO_(2)and pre-industrial experiments of 17 CMIP6 models.The change of effective thermal inertia(ETI)in response to the quadrupling of CO_(2) forcing is the leading mechanism for the seasonal energy transfer mechanism,which acts to store heat temporarily in summer and then release it in winter.The ETI change is strongest over the ice-retreat region,which is also responsible for the strongest AA among the four surface types.The lack of ETI change explains the nearly uniform warming pattern across seasons over the ice-free(ocean)region.Compared to other regions,the ice-covered region shows the maximum inter-model spread in JFM,resulting from a stronger inter-model spread in the oceanic heat storage term.However,the weaker upward surface turbulent sensible and latent heat fluxes tend to suppress the inter-model spread.The relatively small inter-model spread during summer is caused by the cancellation of the inter-model spread in ice-albedo feedback with that in the oceanic heat storage term.

TREATMENT OF METALS, POLYMER FILMS, AND FABRICS WITHA ONE ATMOSPHERE UNIFORM GLOW DISCHARGE PLASMA(OAUGDP) FOR INCREASED SURFACE ENERGY AND DIRECTIONAL ETCHING

Direct exposure of samples to the active species of air generated by a One Atmosphere Uniform Glow Discharge Plasma (OAUGDP) has been used to etch and to increase the surface energy of metallic surfaces, photoresist, polymer films, and nonwoven fab- rics. The OAUGDP is a non-thermal plasma with the classical characteristics of a DC normal glow discharge that operates in air (and other gases) at atmospheric pres- sure. Neither a vacuum system nor batch processing is necessary. A wide range of applications to metals, photoresist, films, fabrics, and polymeric webs can be accom- modated by direct exposure of the workpiece to the plasma in parallel-plate reactors. This technolopy is simple, it produces effects that can be obtained in no other way at one atmosphere; it generates minimal pollutants or unwanted by-products; and it is suitable for individual sample or online treatment of metallic surfaces, wafers, films, and fabrics. Early exposures of solid materials to the OAUGDP required minutes to produce rela- tively small increases of surface energy. These durations appeared too long for com- mercial application to fast-moving webs. Recent improvements in OAUGDP gas com- position, power density, plasma quality, recireulating gas flow, and impedance match- ing of the power supply to the parallel plate plasma reactor have made it possible to raise the surface energy of a variety of polymeric webs (PP, PET PE etc.) to levels of 60 to 70 dynes/cm with one second of exposure. In air plasmas, the high surface ener- gies are not durable, and fall to 50 dynes/cm after periods of weeks to months. Here, we report the exposure of metallic surfaces, photoresist, polymeric films, and nonwo- ven fabrics made of PP and PET to an impedance matched parallel plate OAUGDP for durations ranging from one second to several tens of seconds. Data will be re- ported on the surface energy, wettability, wickability, and aging effect of polymeric films and fabrics as functions of time of exposure, and time after exposure; the rate and uniformity of photoresist etching; and the production of sub-micron structures by OAUGDP etching at one atmosphere.

Contrasting Characteristics of the Surface Energy Balance between the Urban and Rural Areas of Beijing

A direct comparison of urban and rural surface energy balances, as well as a variety of other variables including incoming shortwave/longwave radiation and aerosol optical depth, is conducted for the Beijing metropolitan area. The results indicate that, overall, the urban area receives a smaller amount of incoming shortwave radiation but a larger amount of incoming longwave radiation. However, comparisons in the aerosol optical depth and cloud fraction at the two locations suggest that neither aerosol optical depth nor cloud fraction alone can explain the difference in the incoming shortwave radiation. The urban–rural differences in the incoming longwave radiation are unlikely to be caused by the presence of more abundant greenhouse gases over the urban area, as suggested by some previous studies, given that water vapor is the most dominant greenhouse gas and precipitable water is found to be less in urban areas. The higher incoming longwave radiation observed over the urban area is mostly likely due to the higher temperatures of the ambient air. The urban area is also found to always produce higher sensible heat fluxes and lower latent heat fluxes in the growing season. Furthermore, the urban area is associated with a larger amount of available energy（the sum of sensible and latent heat fluxes） than the rural area, except in May and October when evapotranspiration in the rural area significantly exceeds that in the urban area. This study provides observational evidence of urban–rural contrasts in relevant energy-balance components that plausibly arise from urban–rural differences in atmospheric and land-surface conditions.

Solar energy conversion on g-C3N4 photocatalyst:Light harvesting,charge separation,and surface kinetics

Photocatalysis. which utilizes solar energy to trigger chemical reactions, is one of the most desirable solar-energy-conversion approaches. Graphitic carbon nitride （g-C3N4）. as an attractive metal-free photocatalyst, has drawn worldwide research interest in the area of solar energy conversion due to its easy synthesis, earth-abundant nature, physicochemical stability and visible-light-responsive properties. Over the past ten years, g-C3N4 based photocatalysts have experienced intensive exploration, and great progress has been achieved. However, the solar conversion efficiency is still far from industrial applications due to the wide bandgap, severe charge recombination, and lack of surface active sites. Many strategies have been proposed to enhance the light absorption, reduce the recombination of charge carriers and accelerate the surface kinetics. This work makes a crucial review about the main contributions of various strategies to the light harvesting, charge separation and surface kinetics of g-C3N4 photocatalyst. Furthermore, the evaluation measurements for the enhanced light harvesting, reduced charge recombination and accelerated surface kinetics will be discussed. In addition, this review proposes future trends to enhance the photocatalytic performance of g-C3N4 photocatalyst for the solar energy conversion.

An Assessment of Storage Terms in the Surface Energy Balance of a Subalpine Meadow in Northwest China

The heat storage terms in the soil-vegetation-atmosphere system may play an important role in the surface energy budget.In this paper,we evaluate the heat storage terms of a subalpine meadow based on a ficld experiment conducted in the complex terrain of the eastern Qilian Mountains of Northwest China and their impact on the closure of the surface energy balance under such non-ideal conditions.During the night, the average sum of the storage terms was -5.5 W m,which corresponded to 10.4%of net radiation.The sum of the terms became positive at 0730 LST and negative again at about 1500 LST,with a maximum value of 19 W mobserved at approximately 0830 LST.During the day,the average of the sum of the storage terms was 6.5 W m,which corresponded to 4.0%of net radiation.According to the slopes obtained when linear regression of the net radiation and partitioned fluxes was forced through the origin,there is an imbalance of 14.0%in the subalpine meadow when the storage terms are not considered in the surface energy balance.This imbalance was improved by 3.4%by calculating the sum of the storage terms.The soil heat storage flux gave the highest contribution(1.59%),while the vegetation enthalpy change and the rest of the storage terms were responsible for improvements of 1.04%and 0.77%,respectively.

Surface energy balance on the Antarctic plateau as measured with an automatic weather station during 2014

AWS data during 2014 collected at PANDA-N station, on the East Antarctic Plateau, are analysed. Net Short Wave Radiation(QSWR), net Long Wave Radiation(QLWR), sensible(QH), latent(QL) and subsurface or ground(QG) heat fluxes are computed. Annual averages for QSWR, QLWR, QH, QL and QG of 19.65,-49.16, 26.40,-0.77 and 3.86 W·m-2 were derived based on an albedo value of 0.8. QSWR and QH are the major sources of heat gain to the surface and QLWR is the major component of heat loss from the surface. An i terative method is used to estimate surface temperature in this paper;surface temperature of snow/ice is gradually increased or decreased, thereby changing longwave radiation, sensible, latent and subsurface heat fluxes, so that the net energy balance becomes zero. Mass loss due to sublimation at PANDA-N station for 2014 is estimated to be 12.18 mm w.e.·a-1;and mass gain due to water vapour deposition is estimated to be 3.58 mm w.e.·a-1. Thus the net mass loss due to sublimation/deposition is 8.6 mm w.e.·a-1. This study computes surface energy fluxes using a model, instead of direct measurements. Also there are missing data especially for wind speed, though 2 m air temperature data is almost continuously available throughout the year. The uncertainties of albedo, wind speed and turbulent fluxes cause the most probable error in monthly values of QLWR, QH, QL, QG and surface temperature of about ±4%, ±20%, ±50%, ±11% and ±0.74 K respectively.