Theoretical Investigation Research Articles

Elucidating Black α-CsPbI3 Perovskite Stabilization via PPD Bication-Conjugated Molecule Surface Passivation: Ab Initio Simulations.

The cubic α-CsPbI3 phase stands out as one of the most promising perovskite compounds for solar cell applications due to its suitable electronic band gap of 1.7 eV. However, it exhibits structural instability under operational conditions, often transforming into the hexagonal non-perovskite δ-CsPbI3 phase, which is unsuitable for solar cell applications because of the large band gap (e.g., ∼2.9 eV). Thus, there is growing interest in identifying possible mechanisms for increasing the stability of the cubic α-CsPbI3 phase. Here, we report a theoretical investigation, based on density functional theory calculations, of the surface passivation of the α-, γ-, and δ-CsPbI3(100) surfaces using the C6H4(NH3)2 [p-phenylenediamine (PPD)] and Cs species as passivation agents. Our calculations and analyses corroborate recent experimental findings, showing that PPD passivation effectively stabilizes the cubic α-CsPbI3 perovskite against the cubic-to-hexagonal phase transition. The PPD molecule exhibits covalent-dominating bonds with the substrate, which makes it more resistant to distortion than the ionic bonds dominant in perovskite bulks. By contrasting these results with the natural Cs passivation, we highlight the superior stability of the PPD passivation, as evidenced by the negative surface formation energies, unlike the positive values observed for the Cs passivation. This disparity is due to the covalent characteristics of the molecule/surface interaction of PPD, as opposed to the purely ionic interaction seen with the Cs passivation. Notably, the PPD passivation maintains the optoelectronic properties of the perovskites because the electronic states derived from the PPD molecules are localized far from the band gap region, which is crucial for optoelectronic applications.

Isomeric effects on the electron impact scattering for selected five membered heterocyclic ring molecules

We present electron scattering cross-sectional data for selected isomers of the five-membered ring molecules, specifically oxazole and isoxazole, thiazole and isothiazole, and imidazole and pyrazole. The ab-initio R-matrix method, incorporating static exchange polarization approximations, is employed for this calculation from energy range 0.1 eV to 20 eV. Three shape resonances are identified and characterized in each system, consisting of two π* and one σ* shape resonances. Notably, thiazole and isothiazole exhibit additional σ* resonance which is which is at a lower energy than other σ* resonance. The calculated resonance positions align well with available experimental as well as theoretical data. We also performed electronic structure calculations to aid in characterization of resonances. Comparison of the scattering cross-sectional data with their respective isomers reveal marginal differences in the magnitude of the elastic cross section particularly below 1 eV. This discrepancy may be attributed to variations in the long-range electronic dipole contribution to the electron-molecule interaction process. Further, to understand dependency of dipole moment on elastic cross section, we performed a fitting procedure for the elastic cross sections at 0.1 eV with square of the dipole moment of all the five membered ring molecules studied here. The fitting formula so obtained was used to estimate the cross section for other three five membered ring molecules: Furan, Thiophene and Pyrrole. Additionally, total ionization cross sections are computed using the binary-encounter-Bethe (BEB) model, demonstrating nearly identical results when compared with their isomers. Our findings offer insights into the influence of structural changes on the electron scattering data, providing guidance for other theoretical investigations.

Molecular Engineering Strategies of Spectral Matching and Structure Optimization for Efficient Metal-Free Organic Dyes in Dye-Sensitized Solar Cells: A Theoretical Study.

Metal-free organic dyes are promising dyes that can be applied widely in dye-sensitized solar cells (DSSCs). The rational design and selection of dyes with complementary absorption can promote the development of methods that can enhance the utilization of incident light by DSSCs, such as cosensitization and tandem devices. Based on these opinions, the structure of the reported high-performance metal-free organic dye ZL003 is used as a template to design two new metal-free organic dyes, HX-1 and HX-2, by replacing its donor unit with a 2-phenothiazine-phenylamine unit and fusing its three independent π-bridge units into a whole with the aim of driving the red shift and the blue shift of the absorption spectra of ZL003, respectively. Through theoretical investigation, it is demonstrated that the perfect complementary optical absorption of HX-1 and HX-2 can be realized as the shift of the absorption spectra of ZL003 to different directions, which means their feasibility to the application in cosensitization or tandem dye-sensitized solar cells (T-DSSCs). Furthermore, it is hypothesized that HX-1 may be the dye with better photovoltaic performance than ZL003 by modeling their intramolecular charge-transfer (ICT) processes, TiO2 surface adsorption, and photovoltaic parameters. The short-circuit current density (Jsc) and photoelectric conversion efficiency (PCE) of HX-1 are 23.10 mA·cm-2 and 21.26% in theory, compared to those of 20.68 mA·cm-2 and 19.64% in ZL003 at the same computational level, respectively. In view of the complementary optical properties, the combination of HX-1 with HX-2 may be a reasonable option for dyes for the development of a highly efficient cosensitization system or T-DSSCs in the future. In terms of such findings, these two novel metal-free organic dyes may have bright prospects in the research of highly efficient DSSCs, and this work can provide a reference for the design of dyes with complementary absorption through simple structural adjustments of the realistic dyes with high photovoltaic performance.

Theoretical and experimental investigations on a data-driven trajectory planning scheme for dynamic shape control of piezo-actuated compliant morphing structures

Piezo-actuated compliant morphing structures can transmit motion and force via elastic deformation with lower weight, simplified design, and higher accuracy, a typical example is the variable camber wing. However, the rapid shape change of compliant structures is a challenging control problem because it often results in a high level of vibration due to the structural flexibility necessary to achieve the morphing requirement. This study presents a model-free data-driven trajectory planning approach based on spline curves and surrogate-based optimization (SBO) to obtain smooth “rest-to-rest” morphing trajectories. The macro-fiber composite (MFC) patches are used for piezoelectric actuators to generate elastic deformation. The flexible beam and variable camber wing are used for both linear numerical simulation and experimental tests with various nonlinearities and uncertainties. An optimization criterion is proposed to minimize both transient and residual vibrations during the “rest-to-rest” motion. An extraordinarily terminal displacement error function is added to eliminate the effects of the hysteresis and creep of the actuator. The control inputs, i.e., voltage profiles for the MFCs, are defined using cubic spline curves via only a few control points. Then, the optimization problem is solved by employing a Kriging surrogate model-based algorithm integrated with the expected improvement (EI) infilling-sampling criterion, which constructs an efficient algorithm similar to reinforcement learning. The optimal morphing trajectories can be highly efficiently obtained by using only 4 control points and less than 150 samplings. The experimental results of both the plate model and the variable camber wing model show that the proposed method can not only achieve a smooth dynamic morphing trajectory with minimized vibration but also automatically compensate for hysteresis and creep. The proposed method provides an effective means for the rapid realization of an optimized morphing trajectory for compliant morphing structures.

Combined Theoretical and Experimental Investigations: Design, Synthesis, Characterization, and In Vitro Cytotoxic Activity Assessment of a Complex of a Novel Ureacellobiose Drug Carrier with the Anticancer Drug Carmustine

Combined Theoretical and Experimental Investigations: Design, Synthesis, Characterization, and In Vitro Cytotoxic Activity Assessment of a Complex of a Novel Ureacellobiose Drug Carrier with the Anticancer Drug Carmustine

Impact of the chemical insertion of the dimethylamino group on the electronic and optical properties of the 4-(methoxyphenyl acetonitrile) monomer (MPA): a DFT theoretical investigation.

Density functional theory (DFT) calculations on the ground and the first excited state are performed on the modified and unmodified 4-(methoxyphenyl acetonitrile) monomer (referred to as MPA). The modified monomer named MFA is obtained by Knoevenagel condensation of MPA with dimethylformamide dimethyl acetal (DMF-DMA). DFT computations show that the chemical grafting of the dimethylamino group onto the MPA unit induces a great change in the geometric, electronic, and optical properties. Going from MPA to MFA monomer, a great change in the frontier orbitals of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) in the ground and the first excited state is observed. Consequently, a reduction in the energy gap HOMO-LUMO and an enhancement in the absorption and emission properties are observed under the chemical modification. The observed modifications in the electronics and optical properties are the result of the charge transfer appearing between the cyano (C≡N) acceptor group and the dimethylamino (DMF-DMA)-grafted group donor ring. Quantum chemical calculations were performed in the ground and the first excited state using the density functional theory (DFT), and it extends the time-dependent density functional theory (TD-DFT), implemented in the Gaussian 09 software package. The ground state is obtained by optimization of the studied molecular geometries by employing the DFT/M062X/6-31G(d,p) level of theory. The first excited state is obtained by re-optimization of the ground state geometries using the TD-DFT/M062X/6-31G(d,p) level of theory. The contour plots of the frontier orbitals and the molecular electrostatic potential (MEP) maps are obtained from the ground and the first excited state, optimized geometries, and drawn using Gaussview software.

Theoretical investigation of the reaction mechanism of THP oxidative rearrangement catalysed by BBOX.

γ-Butyrobetaine hydroxylase (BBOX) is a non-heme FeII/2OG dependent enzyme that is able to perform two different kinds of catalytic reactions on 3-(2,2,2-trimethylhydrazinium) propionate (THP) to produce distinct catalytic products. Although the structure of BBOX complexed with THP has been resolved, the details of its catalytic mechanism are still elusive. In this study, by employing molecular dynamics (MD) simulations and density functional theory (DFT) calculations, the mechanism of the THP oxidative rearrangement reactions catalysed by BBOX was investigated. Our calculations revealed how the enzyme undergoes a conformational conversion to initiate the catalytic reactions. In the first catalytic step, BBOX performs hydrogen abstraction from the substrate THP as a common non-heme iron enzyme. Due to the structure of the substrate stabilizing the radical species and polarizing the adjacent N-N bond, in the next step, THP takes the pathway for N-N bond homolysis but not regular hydroxyl rebounding. The cleaved ammonium radical could either react with the hydroxyl group on the iron centre of the enzyme or recombine with the other cleaved fragment of the substrate to generate the rearranged product. This study revealed the catalytic mechanism of BBOX, detailing how the enzyme and the substrate regulated the hydroxyl rebound process to generate various products.

Experimental and Theoretical Investigation of Thermal Parameters Influencing the Freezing Process of Ice Cream

Experimental and Theoretical Investigation of Thermal Parameters Influencing the Freezing Process of Ice Cream

A Theoretical Investigation of Coal Fracture Evolution with Hydrostatic Pressure and its Validation by CT

A Theoretical Investigation of Coal Fracture Evolution with Hydrostatic Pressure and its Validation by CT

Theoretical Investigation on the Effective Coupling Optical System between Astigmatic Tapered Diode Laser Beam and Single-Mode Optical Fibers

Theoretical Investigation on the Effective Coupling Optical System between Astigmatic Tapered Diode Laser Beam and Single-Mode Optical Fibers

A Theoretical Investigation on Equilibrium Magnetic Properties in Nanowire Arrays

Abstract The paper focuses on the study of an Ising nanowire array composed of core/shell-structured single nanowires placed at the edges of a square lattice. The phase transition temperature, at which a transition occurs in the magnetic properties, is obtained using effective field theory for two interacting individual nanowires. To understand how the interaction affects the magnetic, we defined the exchange interaction (JR) between the single nanowires. This interaction is assigned both positive and negative values to reveal the ferromagnetic and antiferromagnetic characteristics of the system. Our results revealed that the exchange interaction between individual nanowires significantly influences the magnetic properties of the system.

Shear Mechanism of a Novel SFCBs-Reinforced Composite Shear Connector: Experimental, Theoretical Investigations and Numerical Model

Traditional stud and perfobond leiste (PBL) shear connectors are commonly used as load-transferring components in steel-concrete composite structures. Composite shear connectors fully utilize the advantages of traditional stud and PBL shear connectors. In order to maximize the advantages of composite shear connectors, a novel shear connector for complex environments was proposed. The steel-FRP composite bars (SFCBs) with excellent fatigue resistance and corrosion resistance were introduced to replace the steel bars. This study discussed the failure modes, load–slip curves, and load–strain curves of the composite shear connector. In addition, a finite element analysis (FEA) model was developed to analyze the influence of various factors on its shear behavior. Results showed that compared with traditional composite shear connectors, the introduction of SFCB resulted in a promotion of 7.85% in shear stiffness, and it also led to a significant increase of 63.61% in ductility, further enhancing the mechanical performance. Meanwhile, FEA models were well fitted to the test results, and parametric analysis showed variate effects on shear bearing capacity. In the end, an equation was established to calculate the shear capacity of composite shear connectors, which could provide a reference for further research and engineering applications.

Doppler sensitivity and resonant tuning of Rydberg atom-based antennas

Abstract Radio frequency antennas based on Rydberg atom vapor cells can in principle reach sensitivities beyond those of any conventional wire antenna, especially at lower frequencies where very long wires are needed to accommodate the growing wavelength. They also have other desirable features such as nonmetallic, hence lower profile, elements. This paper presents a detailed theoretical investigation of Rydberg antenna sensitivity, elucidating parameter regimes that could cumulatively lead to 2--3 orders of magnitude sensitivity increase beyond that of currently tested configurations. The key insight is to optimally \emph{combine} the advantages of two well-studied approaches: (i) three laser ``2D star configuration'' setups that, enhanced as well with increased laser power, to some degree compensate for atom motion-induced Doppler broadening, and (ii) resonant coupling between a pair of near-degenerate Rydberg levels, tuned via a local oscillator to the incident signal of interest. The advantage of the star setup is subtle because it only restores overall sensitivity to the \emph{expected} Doppler-limited value, compensating for additional significant off-resonance reductions where differently moving atom sub-populations actually destructively interfere with each other in the net signal. The additional unique advantage of the local oscillator tuning is that it leads to vastly narrower line widths, as low as $\sim$\,10 kHz set by the intrinsic Rydberg state lifetimes, rather than the typical $\sim$\,10 MHz scale set by the core state lifetimes. Intuitively, with this setup the two Rydberg states may be tuned to act as an independent high-q cavity, a point of view supported through a study of the frequency-dependence of the antenna resonant response. There are a number of practical experimental advances, especially larger $\sim$\,1 cm laser beam widths, required to suppress various extrinsic line broadening effects and to fully exploit this ``Rydberg superheterodyne'' response.

Experimental and Theoretical Investigation of the Inhibitor Efficiency of Eucalyptus globulus Leaf Essential Oil (EuEO) on Mild Steel Corrosion in a Molar Hydrochloric Acid Medium

As a corrosion inhibitor for mild steel in a molar hydrochloric acid medium, we investigated the potential of Eucalyptus globulus essential oil (EuEO). Through electrochemical impedance spectroscopy (EIS), potentiodynamic polarization curves, and theoretical methods, including DFT/B3LYP 6-31G (d, p) and Monte Carlo simulations, the interactions between the EuEO components and the steel surface were analyzed. D-Allose, Betulinaldehyde, and Uvaol were identified as the major active compounds in the GC-MS analysis. The experimental results showed that EuEO reached an inhibitory efficiency as high as 97% at a 1 g/L concentration. The findings suggest that EuEO operates as a mixed-type inhibitor, reducing both cathodic and anodic reactions, as well as building up a protective coating on the steel surface. Simulations also confirmed that EuEO molecules function as electron donors and acceptors, enhancing corrosion resistance.

The Structure of Carbon Dioxide at the Air-Water Interface and its Chemical Implications.

The efficient reduction of CO2 into valuable products is a challenging task in an international context marked by the climate change crisis and the need to move away from fossil fuels. Recently, the use of water microdroplets has emerged as an interesting reaction media where many redox processes which do not occur in conventional solutions take place spontaneously. Indeed, several experimental studies in microdroplets have already been devoted to study the reduction of CO2 with promising results. The increased reactivity in microdroplets is thought to be linked to unique electrostatic solvation effects at the air-water interface. In the present work, we report a theoretical investigation on this issue for CO2 using first-principles molecular dynamics simulations. We show that CO2 is stabilized at the interface, where it can accumulate, and that compared to bulk water solution, its electron capture ability is larger. Our results suggest that reduction of CO2 might be easier in interface-rich systems such as water microdroplets, which is in line with early experimental data and indicate directions for future laboratory studies. The effect of other relevant factors which could play a role in CO2 reduction potential is discussed.

Role of Bi/Te co-dopants on the thermoelectric properties of SnSe polycrystals: an experimental and theoretical investigation

AbstractA sustainable solution to the energy crisis may be found in thermoelectric materials and generators, capable of transforming thermal energy into electrical energy or vice versa. SnSe is one of the emerging thermoelectric materials with distinctive properties. The main advantages of this compound are earth-abundant, inexpensive, non-toxic and it is also known for its high thermoelectric performance. Here we prepared Bi/Te co-doped SnSe polycrystals; whereas, Bi and Te are added with different compositions such as (x = 0.0,0.02,0.04,0.06 and y = 0.03) in (Sn1-xBixSe1-YTeY) matrix by using the solid-state reaction method. XRD data confirms the samples belong to the orthorhombic crystal system with the Pnma space group. DFT calculations were used to see structural stability and electronic properties for pure and doped SnSe samples. Temperature-dependent semiconducting behavior of the samples has been demonstrated by electrical resistivity. The Seebeck coefficient, correlated with carrier concentration and mobility, validates the p-type behavior for the pristine samples and the n-type behavior for co-doped samples. The dominant behavior of phonon scattering has been demonstrated by thermal conductivity analysis. After co-doping there is decrement in total thermal conductivity was observed which 1.3 times lower than SnSe. A theoretical calculation was used to validate experimental results to estimate electrical properties, Seebeck coefficient, specific heat capacity, thermal conductivity, and power factor using Quantum espresso code with Boltzmann transport Equation. 4% Bi-doped sample displayed a significant increment in electrical conductivity and an enhanced Seebeck coefficient, which led to the power factor enhancement of approximately 2.0 times in contrast to the pristine sample and enhanced ZT of about 0.055 which is 3.43 times higher than the pristine SnSe. Graphical abstract

Modified calculation on shear stress of girder bridges with corrugated steel webs

The study examines the shear behaviors in girder bridges with corrugated steel webs (CSWs) considering different boundary constraints through theoretical analysis, experimental investigation, and numerical simulation. The accordion effect significantly amplifies shear deformation in CSWs at support locations. The substantial difference in shear stiffness between the CSWs and the concrete slabs constrains the shear deformation of CSWs, resulting in the generation of additional shear force within the CSWs. Therefore, the existing basic shear method is inaccurate for calculating shear stress in CSWs because it neglects this influencing factor. The study proposes an advanced formula for accurately predicting shear stresses near the supports of a cantilever prismatic girder bridge with CSWs by incorporating the additional shear forces induced by the shear deformation of CSWs. Theoretical analysis has revealed that the expression and magnitude of the additional shear force are correlated with the boundary conditions of the girder bridge. The study formulates expressions for the additional shear force induced by shear deformation in girder bridges with CSWs, considering various boundary conditions such as cantilever, simply supported, fixed-end, and continuous spans. It contributes to further enhancing the analytical method for calculating shear stress in prismatic girder bridges with CSWs, accommodating diverse support constraint conditions. The findings have practical implications for guiding the shear design of girder bridges with CSWs under various support systems.

Direct flipping dynamics and quantized enrichment of chirality at single-molecule resolution.

Chirality is an important aspect of nature, and numerous macroscopic methods have been developed to understand and control chirality. For the chiral tertiary amines, their flexible flipping process makes it possible to achieve high chiral controllability without bond formation and breaking. Here, we present a type of stable chiral single-molecule devices formed by tertiary amines, using graphene-molecule-graphene single-molecule junctions. These single-molecule devices allow real-time, in situ, and long-time measurements of the flipping process of an individual chiral nitrogen center with high temporal resolution. Temperature- and bias voltage-dependent experiments, along with theoretical investigations, revealed diverse chiral intermediates, indicating the regulation of the flipping dynamics by energy-related factors. Angle-dependent measurements further demonstrated efficient enrichment of chiral states using linearly polarized light by a symmetry-related factor. This approach offers a reliable means for understanding the chirality's origin, elucidating microscopic chirality regulation mechanisms, and aiding in the design of effective drugs.

Chemistry of Cyclo[18]Carbon (C18): A Review.

Carbon-based allotropes are propelling a technological revolution in communication, sensing, and computing, concurrently challenging fundamental theories of the previous century. Nevertheless, the demand for advanced carbon-based materials remains substantial. The crux lies in the efficient and reliable engineering of novel carbon allotrope. Although C18 has undergone theoretical and experimental investigation for an extended period, its preparation and direct observation in the condensed phase occurred only recently through STM/AFM techniques. The distinctive cyclic ring structure and the dual 18-center π delocalization character introduce various uncommon properties to C18, rendering it a subject worthy of in-depth exploration. In this context, this review delves into past developments contributing to the state-of-the-art understanding of C18 and provides insights into how future endeavours can expedite practical applications. Encompassing a broad spectrum, this review comprehensively investigates almost all facets of C18, including geometric characteristics, electron delocalization, bonding nature, aromaticity, reactivity, electronic excitation, UV/Vis spectrum, intermolecular interaction, response to external fields, electron affinity, ionization, and other molecular properties. Moreover, the review also outlines representative strategies for the direct synthesis and characterization of C18 using atom manipulation techniques. Following this, C18-based complexes are summarized, and potential applications in catalysis, electrochemical devices, optoelectronics, and sensing are discussed.

Cholesterol Nanofiber Patches with Sustainable Oil Delivery Eliminate Inflammation in Atopic Skin.

Atopic skin is dry and itchy and lacks integrity. Impaired skin barrier results from altered lipid composition of the skin. A crucial skin lipid, cholesterol, provides flexibility and homeostasis of the cell membranes' lipid bilayer. Cholesterol-based creams and natural oils, especially blackcurrant seed oil, are beneficial for skin care as they hydrate the skin and improve its integrity. The major atopic symptom, skin dryness, can be overcome by the application of porous patches enhanced with cholesterol and natural oil. The base of the patches is constructed of polyimide (PI) nanofibers with cholesterol coatings and externally added blackcurrant seed oil. The presence of cholesterol in PI mats hinders the passage of oil through the patches to the skin, resulting in sustained and prolonged skin hydration. The theoretical and numerical investigations of oil dynamics in porous mats confirmed the experimental results, showing a prolonged skin hydration effect up to 6 h. Additionally, as demonstrated by in vivo tests on atopic mice, cholesterol patches lower serum immunoglobulin E levels and expression of proinflammatory cytokines in the skin, thereby accelerating skin healing. Our results hold great promise for the long-term application of the patches in atopic dermatitis treatment.