Semi-empirical Approach Research Articles

Influence of hygrothermal aging on the lifetime and mechanical properties of GFRP/Al adhesive joints

The study aimed to investigate the impact of hygrothermal aging on the degradation of mechanical properties and predict the lifetime of adhesive joints between aluminum alloy (AA6061) and glass fiber-reinforced epoxy (GFRP) composites. The adhesive joints were prepared in a single lap joint (SLJ) configuration and subjected to hygrothermal conditions to induce aging. Immersion tests were conducted at a water temperature of 70°C with varying aging periods (10, 18, 40, 54, 60, and 75 days) to assess the long-term performance and predict the lifetime of the joints. The tensile and shear strength of the adhesive joints were evaluated using a tensile test. The test was performed at room temperature (RT) with a speed rate of 1.3 mm/min. Among the different methods available for lifetime prediction, a semi-empirical approach was selected to analyze the changes in the mechanical properties of the adhesive joints. A comprehensive comparison was made between aged and unaged specimens. The experimental results revealed a reduction in the ultimate tensile and shear strength of the adhesive bonds over the 75-day aging period. The semi-empirical relationship used for long-term durability prediction of adhesive joint structures indicated a 78% decrease in ultimate tensile strength for the adhesive joints over a one-year aging period. This highlights the significant influence of hygrothermal aging on the mechanical properties of the investigated adhesive joints. During the aged periods, various failure modes were observed, including adhesive failure, cohesive failure, and structural failure.

Layer-by-layer WS2-Cr heterojunction as a positive working electrode material for high-performance supercapattery applications

This study investigates the impact on the electrochemical performance of pristine sputtered WS2 through the strategic integration of a highly conductive chromium interfacial layer. This study involves the fabrication of two different samples via magnetron sputtering: type I, WS2-sputtered and type II, WS2/Cr (sputtering of Cr as an interfacial layer between sputtered-WS2 and NF). Afterward, structural, topographic and elemental composition of as-synthesized samples were inspected via XRD, SEM, Raman, and EDX. Following this, the energy storage performance were evaluated by employing CV, GCD, and EIS in three and two electrode assembly sequentially. In three electrode testing WS2 and WS2/Cr exhibited the specific capacity (Qs) of 661.79C g−1 and 1600C g−1 at 3 mV/s along with the capacity retention of 61.37 % (WS2) and 83.04 % (WS2/Cr), respectively. Similarly, through GCD WS2 shows the Qs of 637.34C g−1 at 0.8 A/g conversely, WS2/Cr exhibited the Qs of 1220C g−1 at 1.3 A/g. Besides, the WS2/Cr demonstrated long-term longevity (capacity retention of 83.13 %) after 5000 GCD cycles. Based on exclusive electrochemical performance of type II of two samples, an asymmetric battery-type hybrid supercapacitor (WS2/Cr//AC) was fabricated by incorporating WS2/Cr and activated carbon (AC) as working and counter electrodes. WS2/Cr//AC revealed the Qs of 352C g−1 (785F g-1) at 0.7 A/g. Besides, it deliberately delivered 81 Wh kg−1 and 1750 W kg−1 energy and power. The device exhibits excellent cyclic stability by maintaining its capacity after 5000 GCD cycles and illustrated 87.30 % capacity retention. Following that, semi-empirical approach was applied to quantify the capacitive and diffusive currents’ contribution in overall device’s performance. The results highlight that WS2/Cr hold colossal potential to fill the proficiency gap between presently keep-going devices and stern demands of future energy storage applications.

Effects of temperature, relative humidity and soil organic carbon content on soil-air partitioning coefficients of volatile PFAS.

Soil-air partitioning coefficient (KSA) values are often used to assess the environmental fate of organic contaminants in soil. Till now, sufficient KSA values have not yet been measured for many compounds of interest, including some emerging pollutants such as volatile PFAS. Moreover, the effects of environmental factors such as temperature, relative humidity and soil organic carbon content on KSA of volatile PFAS are also unclear. In this study, the KSA values of target volatile PFAS were measured under various temperature (20-40 °C), relative humidity (30-100 %) and soil organic carbon content (2.1 %-8.0 %) using a modified solid-phase fugacity meter. The results showed that higher temperatures, higher relative humidity and lower organic carbon content in soil may accelerate the diffusion of target volatile PFAS. Furthermore, the KSA measurements were used to derive a multiple linear regression model to depict the relationship between logKSA and temperature, relative humidity, soil organic carbon content and PFAS-specific logKOA. When compared with the predictions obtained from semi-empirical model, we argued that the multiple linear regression model is more robust and easier to implement for target volatile PFAS or other emerging volatile PFAS than the semi-empirical approach to help depict the diffusion process at target volatile PFAS contaminated sites.

Semi-empirical terramechanics modelling of rough terrain represented by a height field

Dynamic simulations of various types of off-road vehicles, from planetary rovers to agricultural equipment, have long relied on well-established semi-empirical terramechanics models. While these models do have drawbacks and reliability issues that have been addressed by numerous works in the decades since the models were first introduced, semi-empirical approaches remain one of the few ways to simulate realistic wheel-soil interaction in real-time. One of their drawbacks is their assumption that the terrain is a flat plane. The models work by integrating normal and shear stresses along the wheel-terrain contact patch. The normal stress at each point along the contact patch is determined using an equation that computes soil pressure based on semi-empirical parameters, the dimensions of the wheel and the sinkage, which is determined based on the distance between the point and the plane that defines the terrain. Other works simplify the rough terrain contact problem by defining an equivalent contact plane at each time step in order to continue to be able to use semi-empirical models - modified to work with slanted planes - to compute the interaction forces. In this work, we propose a new, modified version of the semi-empirical model in which interaction forces for a wheel travelling on rough terrain can be computed without the need to use an equivalent contact plane. To highlight the advantages of our proposed approach, we compare our simulation results to the results of simulations using an existing approach for modelling a wheel travelling over rough terrain using traditional semi-empirical models.

Theoretical Studies of the Electronic and Thermoelectric Properties of PrIn3 and NdIn3 in Cubic Phase

The electronic and thermoelectric properties of AB3 (A =Pr, Nd and B=In) materials (crystallizing in the cubic structure) having space group Pm-3m (221) are studied using B3PW91 hybrid functional through the Full-Potential Linear Augmented Plane Wave (FP-LAPW) approach within the framework of Density Functional Theory (DFT). The calculated lattice parameters for PrIn3 and NdIn3 are 4.5668 Å and 4.5539 Å respectively. Electron-electron correlation effect is due to the 4f orbitals present in these materials and therefore, with the use of B3PW91 hybrid functional, band structure and density of states are calculated. When analyzing electron charge density, these materials showed a stronger ionic character. Band structure and density of state analysis confirms the metallic nature of the materials. Using the semi-empirical Boltzmann approach implemented in the BoltzTraP code, the thermoelectric parameters, such as Seebeck coefficient, figure of merit, electrical conductivity per relaxation time, and electronic thermal conductivity per relaxation time as a function of chemical potential, were computed at 500 K temperature gradient. PrIn3 showed highest Seebeck coefficient value, 50.68 μV/K among these compounds. The peak value of electrical conductivity per relaxation time and electronic thermal conductivity per relaxation time among these compounds is calculated for NdIn3 is 2.43 x 1020 1/Ωms and 22.50×1014 W/mKs.

Increased projected changes in quasi-resonant amplification and persistent summer weather extremes in the latest multimodel climate projections

High-amplitude quasi-stationary atmospheric Rossby waves with zonal wave numbers 6–8 associated with the phenomenon of quasi-resonant amplification (QRA) have been linked to persistent summer extreme weather events in the Northern Hemisphere. QRA is not well-resolved in current generation climate models, therefore, necessitating an alternative approach to assessing their behavior. Using a previously-developed fingerprint-based semi-empirical approach, we project future occurrence of QRA events based on a QRA index derived from the zonally averaged surface temperature field, comparing results from CMIP 5 and 6 (Coupled Model Intercomparison Project). There is a general agreement among models, with most simulations projecting substantial increase in QRA index. Larger increases are found among CMIP6-SSP5-8.5 (42 models, 46 realizations), with 85% of models displaying a positive trend, as compared with 60% of CMIP5-RCP8.5 (33 models, 75 realizations), with a reduced spread among CMIP6-SSP5-8.5 models. CMIP6-SSP3-7.0 (23 models, 26 realizations) simulations display qualitatively similar behavior to CMIP6-SSP5-8.5, indicating a substantial increase in QRA events under business-as-usual emissions scenarios, and the results hold regardless of the increase in climate sensitivity in CMIP6. Projected aerosol reductions in CMIP6-SSP3-7.0-lowNTCF (5 models, 16 realizations) lead to halting effect in QRA index and Arctic Amplification during the 1st half of the twenty-first century. Our analysis suggests that anthropogenic warming will likely lead to an even more substantial increase in QRA events (and associated summer weather extremes) than indicated by past analyses.

Analytical Model for the In-Plane Lateral Capacity of Unreinforced Masonry Walls Based on Effective Compression Zone Failure Mechanism

ABSTRACT This study proposes a simplified theoretical model to predict the in-plane lateral capacity of unreinforced masonry (URM) walls, addressing limitations in current design guidelines based on semi-empirical approaches. Masonry walls are conceptualized as macroscale units subjected to vertical and lateral loads, with failure mechanisms governed by the effective compression zone. The model applicability is evaluated against comprehensive URM datasets and compared with existing guidelines. The results indicated the outperformance of the proposed model compared to existing guidelines. Additionally, a parametric study explores the influence of primary design parameters on the in-plane lateral capacities of URM walls, offering valuable predictive insights.

Charge injection mediated by inverse micelles in nonpolar solvents: A microscopic model

HypothesisNonpolar solvents with added charge control agents are widely used in various applications, such as E-paper displays. In spite of previous work, the mechanisms governing charge generation in nonpolar liquids, particularly those induced by electrochemical reactions at the liquid-solid interface, are not completely understood. We hypothesize that a physics-based model, according to the modified Butler–Volmer equation, can be used to quantitatively predict the injection of charges and the corresponding currents, in nonpolar solvents with surfactants. Simulation and ExperimentsWe propose a model to describe the migration and charge generation of inverse micelles. In addition to the mechanisms of electromigration, diffusion and charge generation via disproportionation that were introduced in earlier models, we include charge generation via electron injection at the electrodes using a microscopically justified expression as opposed to the previously used semi-empirical approaches. To validate our model, we compare its results to experimental current measurements in a simplified, effectively 1D, geometry. FindingsWe find that the incorporation of both bulk and electrochemical reaction mechanisms in the model can effectively explain the experimental steady-state currents in a wide range of concentrations, voltages (0.5 V-5 V), and cell thicknesses. These numerical results of currents at longer time scales show a steady-state current only when both bulk and electrochemical reactions are taken into account. Moreover, we have observed in our simulation that at low applied voltages, the electric field in the bulk is fully shielded, and the steady-state current in this low-voltage regime is governed by the charge injection at the electrodes. Conversely, when the voltage is high enough and the electric field remains partially unscreened, the bulk disproportionation mechanism dominates the current generation. This also explains why we observe a non-Ohmic behavior where the steady-state currents at high voltages are independent of applied voltage. Hence, by elucidating the physical processes underlying the experimental observations, our model offers a more profound comprehension of charge transport in these systems, which could facilitate advancements in the design of enhanced E-ink displays and smart windows.

Application of a semi-empirical modelling approach to a Two-Stage Rotary CO2 compressor

2-stage Rotary CO2 compressors are currently in use in refrigeration and heat pump applications, including occasionally including vapour injection. The need of correctly assessing the compressor’s efficiency by means of a computationally fast model arises for cycle performance prediction and optimization. In response, an innovation on an existing semi-empirical modelling approach has been introduced in this paper to describe 2-stage Rotary compressors. The model has been validated with experimental data of a CO2 compressor available in open literature, giving maximum errors of around ±3% for mass flow and ±1.82% for power prediction. Calibration of a simplified 1-stage model is also performed to analyse to which extent it is necessary to complexify the model, and to identify key or neglectable modelling elements. It is found that doing this increases the error of the compressor performance prediction. Model analysis has been done to identify the inefficiencies introduced by each physical effect considered.

‘Turn On’ fluorescent imine linked 1,2,3-triazole based chemosensor for detection of mercuric ions

The exorbitant use or erroneous management of metal ions has been incurred with catastrophic pollution of our ecological system, particularly in soil and water bodies, resulting in significant repercussions. Hence, precise identification and analysis of heavy-metal ions in intricate hydrological environments is imperative. Therefore, an imine conjugated 1,2,3-triazole derivative VPT was synthesized, characterized via FTIR, NMR (1H &13C), LCMS spectroscopic techniques and was employed for the exclusive identification of Hg2+ ions in the presence of various other metal ions via UV–Visible and fluorescence spectroscopy. The sensor VPT exhibited binding constant (Ka) value of 2.93 × 104 M−1 and detection limit value of 0.5 × 10−9 M in the ACN:H2O::4:1 medium. The stoichiometric ratio was determined using Job’s plot, which revealed a (1:1) ratio of VPT with Hg2+ ions. In addition, time-dependent, temperature-dependent, and pH titration studies were conducted via U.V-Visible spectroscopy to expand the sensor’s applicability. The viable configurations of probe VPT and its 1:1 stoichiometric with Hg2+ ion were optimized using the B3LYP/6-311G++(d,p)/LANL2DZ levels of theory in the Gaussian 09 program respectively and this semi-empirical quantum mechanics approach demonstrated a reduction in the energy gap confirming the stable formation of [VPT-Hg2+] complex. These insights facilitate the design offluorescent probe VPT for detecting Hg2+ in both environmental and biological context.

Exploring the optical behavior and relative translucency parameter of CAD-CAM resin-based composites, polymer-infiltrated ceramic network, and feldspar porcelain

ObjectivesTo evaluate and compare the optical properties and relative translucency parameter of CAD-CAM restorative materials. MethodsFour CAD-CAM materials were evaluated: Lava Ultimate (LU), Grandio Blocs (GB), VITA Enamic (VE), and VITA Mark II (VM). Disk-shaped samples in shade A2-HT were prepared (n = 10) and polished to 1.00 ± 0.01 mm of thickness. Scattering (S), absorption (K), albedo (a) coefficient, transmittance (T%), light reflectivity (RI), infinite optical thickness (X∞), and radiative transfer coefficients (μa, and μ′S) were calculated using Kubelka-Munk method and Thennadil's semi-empirical approach. Root Mean Square Error (RMSE) and Goodness of Fit (GFC) were used as performance optical behavior. Translucency differences were evaluated using the relative translucency parameter (RTP00) and 50:50 % translucency perceptibility and acceptability thresholds (TPT00 and TAT00). ResultsThe spectral distribution of S, K, T%, RI, and X∞ was wavelength-dependent. GFC and RMSE values indicated good spectral behavior matches and good comparative spectral values for RI in LU-GB, LU-VE, and GB-VE, and for K in VE-VM. VM displayed the highest scattering values across the wavelengths, while VE and VM showed lower absorption at shorter wavelengths. LU and GB had the highest transmittance. The X∞ values indicated that all 1.0 mm thick materials could be influenced by the background. No good spectral match and no good comparative spectral values were found between CAD-CAM materials and anterior bovine maxillary specimens. VM had the lowest RTP00 values with perceptible and unacceptable differences compared to CAD-CAM materials evaluated. SignificanceUnderstanding the optical behavior of different CAD-CAM materials was essential for guiding clinicians in material selection and optimizing their clinical performance. The findings confirm that the different compositions and microstructure impact the optical properties and translucency of CAD-CAM restorative materials.

A semiempirical model for low energy electron–atom transport cross sections: The case of noble gases

A semiempirical approach to describe low energy electron–atom transport cross sections of easy implementation and reproduction is presented. The heart of the model is an energy independent two-parameter potential that was adjusted to reproduce the accurate total cross sections for He, Ne, Ar and Kr, measured with a threshold photoelectron source technique from meV up to 20 eV. Once the potential was conceived, the model was validated by comparing the values obtained for the calculated scattering lengths and phase shifts with the respective quantities previously reported in the literature. We close the article by presenting the momentum transfer and viscosity cross sections. Good agreement is found when compared to the similar data obtained from swarm experiments, from phase shifts according to differential cross section measurements and to the cross sections reported by sophisticated ab initio relativistic many-body calculations. Tables for the phase shifts and cross sections are provided for direct use and applications.

On the Assessment of Reinforced Concrete (RC) Walls under Contact/Near-Contact Explosive Charges: A Deep Neural Network Approach

In recent years, the use of machine learning has been expanded to several fields, with promising advances in structural engineering applications. Deep neural network models have been implemented to predict the structural response of systems under conventional loading. Some of those neural network models are based on datasets containing images, test data, and/or data produced by using finite element models developed for a specific environment. While the accuracy of these models relies on the size and quality of the dataset, their use for blast analysis is rather limited, as publicly available data are scarce or restricted. Reinforced concrete (RC) walls or slabs under blast loading are commonly evaluated for flexural and shear behaviour, for which performance guidelines are widely available. While such response mechanisms are typically associated with the far-field range, the target response is controlled by local failure modes when blast loads are generated by contact or near-contact detonations. This paper introduces the implementation of a neural network model for the response prediction of RC walls subjected to contact and near-contact explosions. The model predicts the damage category (i.e., no damage, spall, and breach) associated with a given explosion scenario. The model is trained using experimental data from multiple test programmes available in open-source literature. It considers several parameters associated with the explosive charge (e.g., type, geometry, charge weight, and standoff) and RC target (e.g., material properties, geometry, and reinforcement). The model is able to accurately predict 81% of the total breached specimens, 66% of the total spalled specimens, and 71% of the full set of non-damaged specimens, with an overall accuracy of 72%, with precision and recall ranging from 60 to 76% and 66 to 81%, respectively. The current model is shown to be a significantly better predictor of the damage category than the semi-empirical approach outlined in UFC 3-340-02, making it a promising tool that can be improved with the inclusion of more experimental data.

Atomic structure and Stark width calculation for Cl III ion

In this work, we calculated Stark broadening widths of several doubly-ionized chlorine Cl III spectral lines using the modified semi-empirical approach. The theoretical values of Stark widths are calculated using term energies and oscillator strengths of Cl III from the AUTOSTRUCTURE atomic structure code. We compared the calculated Stark widths with available data from the literature. If we need to interpolate these Stark widths at different temperatures for the studied transitions of Cl III, we use a simple and accurate fitting formula based on a least-squares fitting method.

Theoretical Analysis of Superior Photodegradation of Methylene Blue by Cerium Oxide/Reduced Graphene Oxide vs. Graphene.

Density functional theory and a semi-empirical quantum chemical approach were used to evaluate the photocatalytic efficiency of ceria (CeO2) combined with reduced graphene oxide (rGO) and graphene (GP) for degrading methylene blue (MB). Two main aspects were examined: the adsorption ability of rGO and GP for MB, and the separation of photogenerated electrons and holes in CeO2/rGO and CeO2/GP. Our results, based on calculations of the adsorption energy, population analysis, bond strength index, and reduced density gradient, show favorable energetics for MB adsorption on both rGO and GP surfaces. The process is driven by weak, non-covalent interactions, with rGO showing better MB adsorption. A detailed analysis involving parameters like fractional occupation density, the centroid distance between molecular orbitals, and the Lewis acid index of the catalysts highlights the effective charge separation in CeO2/rGO compared to CeO2/GP. These findings are crucial for understanding photocatalytic degradation mechanisms of organic dyes and developing efficient photocatalysts.

Quantifying Volume Change in Porous Electrodes via the Multi-Species, Multi-Reaction Model

Automotive manufacturers are working to improve individual cell and overall pack design by increasing their performance, durability, and range, while reducing cost; and active material volume change is one of the more complex aspects that needs to be considered during this process. As the time from initial design to manufacture of electric vehicles is decreased, design work that used to rely solely on testing needs to be supplemented or replaced by virtual methods. As electrochemical engineers drive battery and system design using model-based methods, the need for coupled electrochemical/mechanical models that take into account the active material change utilizing physics based or semi-empirical approaches is necessary[1-9]. In this study[10], we illustrated the applicability of a mechano-electrochemical coupled modeling method considering the multi-species, multi-reaction model as popularized by Verbrugge[11-16] and Baker. To do this, validation tests were conducted using a computer-controlled press apparatus that can control the press displacement and press force with precision. The coupled MSMR volume change model was developed and its applicability to graphite and NMC cells was illustrated. The increased accuracy of the model considering the coupled MSMR volume change approach shows in the importance of accounting for individual gallery volume change behavior on cell level predictions. References T. R. Garrick, K. Kanneganti, X. Huang and J. W. Weidner, J Electrochem Soc, 161, E3297 (2014).T. R. Garrick, Y. Dai, K. Higa, V. Srinivasan and J. W. Weidner, Ecs Transactions, 72, 11 (2016).T. R. Garrick, K. Higa, S.-L. Wu, Y. Dai, X. Huang, V. Srinivasan and J. W. Weidner, J Electrochem Soc, 164, E3592 (2017).T. R. Garrick, X. Huang, V. Srinivasan and J. W. Weidner, J Electrochem Soc, 164, E3552 (2017).D. J. Pereira, J. W. Weidner and T. R. Garrick, J Electrochem Soc, 166, A1251 (2019).D. J. Pereira, M. A. Fernandez, K. C. Streng, X. X. Hou, X. Gao, J. W. Weidner and T. R. Garrick, J Electrochem Soc, 167, 080515 (2020).T. R. Garrick, J. Gao, X. Yang and B. Koch, J Electrochem. Soc., 168 (1) 010530 (2021)D. J. Pereira, A. M. Aleman, J. W. Weidner and T. R. Garrick, J Electrochem Soc, 169, 020577 (2022).T. R. Garrick, Y. Miao, E. Macciomei, M. Fernandez and J. W. Weidner, J Electrochem Soc, 170, 100513 (2023).T. R. Garrick, M. A. Fernandez, M. Verbrugge, C. Labaza, R. Mollah, B. J. Koch, M. Jones, J. Gao, X. Gao and N. Irish, J. Electrochem. Soc., 170 060548 (2023)M. Verbrugge, D. Baker and X. Xiao, J Electrochem Soc, 163, A262 (2016).M. Verbrugge, D. Baker, B. Koch, X. Xiao and W. Gu, J Electrochem Soc, 164, E3243 (2017).D. R. Baker and M. W. Verbrugge, J Electrochem Soc, 165, A3952 (2018).D. R. Baker and M. W. Verbrugge, J Electrochem Soc, 167, 013504 (2019).D. R. Baker, M. W. Verbrugge and W. Gu, J Electrochem Soc, 166, A521 (2019).M. W. Verbrugge, X. Xiao and D. R. Baker, J Electrochem Soc, 167, 080523 (2020).

Assessment of hydraulic performance changes of Dongting Lake after the Three Gorges Reservoir impoundment by a novel semi-empirical approach

Assessment of hydraulic performance changes of Dongting Lake after the Three Gorges Reservoir impoundment by a novel semi-empirical approach

Integral-scale validation of the SCIANTIX code for Light Water Reactor fuel rods

Mechanistic multi-scale modelling holds the potential to inform fuel performance codes by incorporating high-fidelity models, algorithms, parameters, and material properties. In this context, meso-scale codes emerge as valuable tools for developing detailed models and performing separate verification and validation steps. This work focuses on SCIANTIX, an open-source 0D meso-scale code designed to describe the behaviour of gaseous and volatile fission products in nuclear oxide fuel. The code predominantly employs engineering physics-based behavioural models featuring computational times that align with typical fuel performance code requirements. Given the numerical foundation of the code, it is applicable to both stationary and transient conditions. Following a recent work outlining the standalone SCIANTIX (version 2.0) performance and its separate-effect validation database, we present its performance when coupled with fuel performance codes to simulate light water reactor fuel rods. The experiments selected for the comparative analysis constitute an initial integral validation database. The comparison focuses on conventional engineering quantities of interest, such as integral fission gas release, demonstrating the satisfactory performance of the code. Additionally, it highlights the potential advantages of multi-scale modelling over conventional semi-empirical approaches.

Exploring the electrochemical synergy of metal sulfides and metal-organic framework composite as hybrid supercapacitor electrodes

Metal-organic frameworks (MOFs) are promising electrode materials however, they continue to seek improvements in both energy density and electrical conductivity. Within a wide array of available metal nodes and linkers, the task of refining and attaining a profound comprehension of charge storage mechanisms is still to accomplish. Herein nickel sulfide and nickel MOF were synthesized via hydrothermal method, their properties were investigated, and a binary composite was developed due to the high resistance of pristine MOFs. This composite demonstrated exceptional specific capacity of 787.8 C/g at cost of 2.0 A/g. To leverage real-world applications, a supercapattery was fabricated using the NiS/Ni-MOF as the positive electrode material and activated carbon as the negative electrode material. The device possesses maximum specific energy of 64.67 Wh/kg and maximum specific power of 3200 W/kg together with capacity retention of 91 % after 5k charge-discharge cycles. To validate results, semi-empirical approach using Dunn’s model and power law is subjected to investigate the capacitive and diffusive contributions and b-values. This study shows that the binary composites of metallic sulfides with MOFs can possess potentials for their applications in real devices.

A new parameterization of the DFT/CIS method with applications to core-level spectroscopy.

Time-dependent density functional theory (TD-DFT) within a restricted excitation space is an efficient means to compute core-level excitation energies using only a small subset of the occupied orbitals. However, core-to-valence excitation energies are significantly underestimated when standard exchange-correlation functionals are used, which is partly traceable to systemic issues with TD-DFT's description of Rydberg and charge-transfer excited states. To mitigate this, we have implemented an empirically modified combination of configuration interaction with single substitutions (CIS) based on Kohn-Sham orbitals, which is known as "DFT/CIS." This semi-empirical approach is well-suited for simulating x-ray near-edge spectra, as it contains sufficient exact exchange to model charge-transfer excitations yet retains DFT's low-cost description of dynamical electron correlation. Empirical corrections to the matrix elements enable semi-quantitative simulation of near-edge x-ray spectra without the need for significant a posteriori shifts; this should be useful in complex molecules and materials with multiple overlapping x-ray edges. Parameter optimization for use with a specific range-separated hybrid functional makes this a black-box method intended for both core and valence spectroscopy. Results herein demonstrate that realistic K-edge absorption and emission spectra can be obtained for second- and third-row elements and 3d transition metals, with promising results for L-edge spectra as well. DFT/CIS calculations require absolute shifts that are considerably smaller than what is typical in TD-DFT.