Charge Density Distribution Research Articles

Investigation of the Physical Attributes of Sr2GeCrO6, Sr2MgMoO6, Ba2MgMoO6, Ba2ZnMoO6, and Ba2HgWO6 Double Perovskite Oxides

A density functional theory‐based study on the physical properties of significant double perovskite oxides Sr2GeCrO6, Sr2MgMoO6, Ba2MgMoO6, Ba2ZnMoO6, and Ba2HgWO6 has been conducted using the Vienna Ab initio Simulation Package and WIEN2K code. Structural analysis reveals the simple cubic crystal structure of double perovskite oxides. Phonon properties indicate the dynamical stability of Sr2GeCrO6, Ba2MgMoO6, and Ba2ZnMoO6 compounds. The band structure analysis indicates the metallic character of Sr2GeCrO6. However, generalized gradient approximation of Perdew–Burke–Ernzerhof and modified Becke–Johnson both suggest the indirect semiconducting nature of Ba2MgMoO6 and Ba2ZnMoO6. The crystal orbital Hamilton population (–COHP) examination evidences the strongest bonding interactions of O–Ba in these perovskite oxides. Both Ba2MgMoO6 and Ba2ZnMoO6 compounds exhibit p‐type character, as indicated by the partial charge density distributions in the highest occupied molecular orbital and lowest unoccupied molecular orbital (LUMO) orbitals, which govern the band edges near Fermi level. LUMO orbitals are located on Mo and O atoms and are composed of heteronuclear s‐ and p‐type interactions. The investigation comprehensively analyzes calculated optoelectronic properties, including complex dielectric function, optical conductivity, loss function, refractive index, and so on. These parameters are examined in detail, offering profound insights into the materials’ optical and electronic characteristics.

Fabricated S-scheme CoS/CeO2 heterojunction photocatalyst efficiently activates peroxymonosulfate for polyethylene terephthalate plastic degradation: Insight into radicals and electron transfer

Polyethylene terephthalate (PET) plastics are widely utilized, yet they also give rise to significant environmental contamination. In this study, a CoS/CeO2 material with an S-scheme heterojunction was constructed using CoS with CeO2 derived from MOFs and employed for the photocatalytic activation of peroxomonosulfate (PMS) for the degradation of PET. The CoS/CeO2/vis/PMS system demonstrated a degradation rate of up to 95.75 % (weight loss rate) for PET plastic. The performance of this system is much better than that of simple photocatalytic or PMS systems. Photogenerated carriers generated by heterojunctions upon illumination accelerate the fast electron cycling of Co2+/Co3+ through the S-scheme transfer pathway driven by a directional interfacial electric field. This promoted efficient mass transfer in the inhomogeneous phase system (such as SO4•−, e−) and acted as an adsorption activation site for PMS. In-situ X-ray photoelectron spectroscopy (In-situ XPS) and ESR test proved that the electron flow in the heterojunction conforms to the S-scheme mechanism. Density functional theory (DFT) calculations revealed the material of the CoS/CeO2 interface and the successful construction of the modulated electronic structure led to the accumulation of holes on CeO2 and electrons on CoS. Bader analysis on charge density distribution further demonstrated that the formation of the heterojunction decreased the adsorption energy of the PMS on the Co sites, which in turn lowered the energy barrier for the generation of SO4•−. This work would provide a novel solution to the problem of removing plastic pollutants from water, as well as new insight into the construction of S-scheme heterojunctions and the mechanism of photocatalytic PMS activation.

Numerical study on characteristics of spiked electrode electrostatic precipitator

The characteristic of the spiked electrode electrostatic precipitator was numerically studied. The spiked electrode had significant effects on the distribution of electric field and charge density. The electric field and charge density were quite high in the area around the spiked electrode tips while decreased rapidly in other area far from the tips. Complicated electrohydrodynamic flow was observed and strong vortices were formed in the upstream and side areas of the spiked electrode. The gas velocity at the tip of the spiked electrode was as high as 28.1 m/s at the working potential of 45 kV. The working potential was more effective for the removal of large particle. The removal efficiency increased 42.4% for 10 µm particle and 15.2% for 0.25 µm particle as working potential increased from 22.5 kV to 45 kV. Low gas velocity was beneficial to the removal of all size particles. The removal efficiency increased by 10% to 15% for all size particles when the gas velocity decreased from 1.0 m/s to 0.6 m/s.

Mitigating Mercury Accumulation and Enhancing Methylmercury Degradation in Rice: Insights from Zinc-Mercury Antagonism at Molecular Levels.

Zn as an essential element has the potential to protect against mercury (Hg) toxicity in rice. However, the antagonistic effects between Zn and Hg in rice and their mechanisms remain unknown. This study proposed a promising strategy for Zn application to mitigate Hg accumulation and toxicity in rice and revealed the underlying molecular mechanisms. The findings revealed that Zn supplementation significantly reduced the uptake and transportation of both IHg and MeHg in rice, thereby alleviating Hg phytotoxicity. In particular, Zn profoundly mitigated Hg-induced oxidative damage to rice, which was attributed to the redistribution of Hg and Zn in the root and Zn competing for binding sites on glutathione. The co-binding of Zn2+ and HgCH3+ within the same active sites of Zn transporters can promote the transfer of regions with a high charge density distribution at the highest occupied molecular orbital (HOMO) level. This process facilitates proton attack on the Hg-C bond, thereby enhancing MeHg demethylation in rice. By elucidating the molecular mechanisms of Zn, IHg, and MeHg interactions in rice, this study offers new insights for developing efficient strategies to mitigate Hg risks while boosting the Zn content in crops, thereby fortifying food safety.

Investigating the electronic properties and reactivity of polyaniline emeraldine base functionalized with metal oxides

Due to its appealing qualities, such as its miniature size and the ability to modify physical properties through chemical synthesis and molecular design, polymer material offers considerable advantages over traditional inorganic material-based electronics. Conjugate polymers are particularly interesting because of their molecular design capabilities, which enable the synthesis of conducting polymers with a variety of ionization potentials and electron affinities (EA), and their ability to control the energy gap and electronegativity (χ). Accordingly, density functional theory (DFT) at the B3LYP/SDD model was used to present possible interactions between polyaniline (PANi) and both alkali and heavy metal oxides. Total dipole moment (TDM), HOMO–LUMO band gap energy (ΔE), ionization energy (IE), EA, chemical hardness (η), chemical potential (μ), electrophilicity index (ω), chemical softness (S), and χ are calculated. TDM of PANi increased while ΔE decreased due to functionalization. The distribution of electronic charge density in molecular electrostatic potential (MESP) maps together with the results of ω reflected the electrophilic nature. The obtained results confirmed that the addition of metal oxides significantly improves the TDM, ΔE, and reactivity descriptors. A strong correlation between the experimental and calculated IR spectra was observed. Additionally, PANi–2MgO and PANi–2MnO model molecules exhibited the highest reactivity. Accordingly, PANi functionalized with MgO and MnO are promising candidates for energy storage devices.

Tuning Electron-Transfer Driving Force in Photosynthetic Special Pair Models.

Visible-light excitation of a family of bimetallic ruthenium polypyridines with the formula [RuII(tpy)(bpy)(𝜇-CN)RuII(py)4L]n+ (RuRuLn+), where L = Cl-, NCS-, DMAP and ACN, was used to prepare photoinduced mixed-valence (PI-MV) MLCT states as models of the photosynthetic reaction center. Ultrafast transient absorption spectroscopy allowed to monitor photoinduced IVCT bands between 6000 and 11000 cm-1. Mulliken spin densities resulting from DFT and (TD)DFT computations revealed the modulation of the charge density distribution depending on the ligand substitution pattern. Results are consistent with PI-MV systems ranging from non-degenerate Class II to degenerate Class III, with electronic couplings between 1000 and 3500 cm-1.These findings guide the control electron localization-delocalization in charge-transfer/charge-separated excited states, like those involved in the photosynthetic reaction center.

Gaussian-Transform for the Dirac Wave Function and its Application to the Multicenter Molecular Integral Over Dirac Wave Functions for Solving the Molecular Matrix Dirac Equation

Gaussian-transform formula is derived for the Dirac wave function. Using it, one can derive the multicenter molecular integral over Dirac wave functions for any physical quantity. As the first application of it, multicenter molecular integrals over Dirac wave functions are derived for the homogeneous charge density distribution model and the Gauss-type charge density distribution model. Such integrals are necessary for solving the gauge-invariant molecular matrix Dirac equation with using the restricted magnetic balance.

Manipulation of ionic transport behavior in smart nanochannels by diffuse bipolar soft layer

Soft bipolar nanochannels provide distinct and valuable understanding of the intricate relationship among shape, charge distribution, concentration, and flow dynamics. This study investigates the intriguing realm of nanoscale structures, where two distinct configurations of soft layers with varying charges provide an intricate but appealing setting for the movement and management of ions, as well as the regulation and control of ionic species in nanochannels with five various geometries. It generates cylindrical, trumpet, dumbbell, hourglass, and conical forms. The nanochannels are coated with a diffuse polyelectrolyte layer, and the charge density distribution in the soft layer is described using the soft step distribution function. To enhance accuracy, the impact of ionic partitioning is taken into account. To investigate the effect of soft layer polarity, two types were considered: Type I and Type II. In Type I, the negative pole is at the start, while in Type II, the positive pole is at the start. Thus, Type I features a bipolar soft layer arrangement of negative–positive (NP), whereas Type II has a positive–negative (PN) configuration. The research was conducted under stationary conditions using the finite element method, Poisson–Nernst–Planck, and Navier–Stokes equations. By manipulating variables such as the arrangement order, charge density of the soft layer, and bulk concentration, a numerical analysis was performed to investigate the impact of these variables on current–voltage parameters. The results demonstrate the soft layer with a positive charge serves as a more effective receiver layer for generating greater rectification. For instance, the dumbbell-shaped nanochannel exhibits a rectification of 2046 at a concentration of 1 mM and the lowest charge density in the soft layer. From an alternative perspective, the conductivity in bipolar nanochannels is significantly influenced by the bulk concentration. The study's findings on the fundamental principles of soft bipolar nanochannels have profound implications for the diverse applications of nanochannels. The capacity to regulate and manipulate ion transport through these nanochannels can result in enhanced efficiency, selectivity, and performance in various processes.

Introducing built-in electric field and spatially separated reactive sites in asymmetric crystalline g-C3N4 for robust photocatalytic hydrogen generation

Constructing arobust internal electric field within photocatalysts is a crucial strategy for propelling the reverse migration of photocarriers and ensuring theeffective occurrence of respective reduction and oxidation reactions. Herein, we synthesized a crystalline g-C3N4 with anasymmetrical structure via introducing a small molecule 2-aminopyrimidine-4,6-diol (AP) and cyano groups on heptazine ring units. The optimized sample (ACNM-3) is endowed with an uneven distribution of charge density and a large dipole moment, thus forming a built-in electric field, which is beneficial for charge separation and migration in space. In-situ XPS and DFT theoretical calculations demonstrate that Pt acts as the reduction site loaded on the inserted AP and the C site of its adjacent heptazine ring, while the oxidation sites are around the heptazine rings containing the cyano groups and the N sites of its adjacent heptazine rings. Such spatially separated redox sites enable ACNM-3 to continuously and robustly trigger proton reduction and TEOA oxidation reactions. Thus, ACNM-3 exhibits an outstanding and stable photocatalytic H2 production rate ofup to 14.19 mmol/g/h, which is over 16 times that of bulk g-C3N4. This work provides a synergistic strategy of internal electric field and catalytic site modulation to synthesize efficient and robust photocatalysts, illuminating the way for the application of photocatalytic H2 production.

First-principles study of WS2 monolayer decorated with noble metals (Pt, Rh, Ir) as the promising candidates to detect nitrogenous poisonous gases

Rapid identification of nitrogenous toxic gases (NPGs, including NO, NO2, NH3, and HCN) emitted from industrial processes is essential for environmental preservation. In this research, the first-principles calculations have been employed to systematically investigate the adsorption behavior and sensing characteristics of Pt, Rh, Ir-modified WS₂ monolayers (Pt-WS2, Rh-WS2, and Ir-WS2) towards these NPGs, with the aim of assessing the potential of WS2-based gas sensors for NPG detection. The results show that Pt, Rh, and Ir atoms can be stably anchored on the WS2 surface, enhancing its chemical stability and the quantity of active sites. Additionally, the strong orbital hybridization between these noble metal atoms and gas molecules enhances the adsorption capacity of WS₂, markedly boosting the adsorption potency of these modified substances towards NPGs (Eads≥−0.69 eV) while maintaining high selectivity toward NPGs in the presence of interfering gases (H2O, N2, CO2). Analysis of the density of states, charge density distribution, and electron localization function indicates weak chemical adsorption of HCN on Pt-WS2, Rh-WS2, and Ir-WS2, while strong chemical adsorption is observed for NO, NO2, and NH3. Furthermore, the adsorption of NO and NO₂ leads to significant band gap changes (∆Eg > 30 %) of Pt-WS2, Rh-WS2, and Ir-WS2, and the response of work function to NH₃ and HCN adsorption is similarly pronounced (∆Φ > 15 %). Finally, analysis of recovery time indicates that Pt-WS2 and Rh-WS2 can serve as work function gas sensors for HCN and as adsorbents for NO, NO2, and NH3 at room temperature, whereas Ir-WS2 can function as a reusable gas sensor for the effective detection of HCN at high temperature. This investigation establishes a robust theoretical framework for the development and manufacture of high-performance WS₂-based gas sensors.

Elastic constants from charge density distribution in FCC high-entropy alloys using CNN and DFT

While high-entropy alloys (HEAs) present exponentially large compositional space for alloy design, they also create enormous computational challenges to trace the compositional space, especially for the inherently expensive density functional theory calculations (DFT). Recent works have integrated machine learning into DFT to overcome these challenges. However, often these models require an intensive search of appropriate physics-based descriptors. In this paper, we employ a 3D convolutional neural network over just one descriptor, i.e., the charge density derived from DFT, to simplify and bypass the hunt for the descriptors. We show that the elastic constants of face-centered cubic multi-elemental alloys in the Ni–Cu–Au–Pd–Pt system can be predicted from charge density. In addition, using our recent PREDICT approach, we show that the model can be trained only on the charge densities of simpler binary and ternary alloys to effectively predict elastic constants in complex multi-elemental alloys, thereby further enabling easier property-tracing in the large compositional space of HEAs.

Quantum Chemical Analysis of the Molecular and Fragment Ion Formation of Butyrophenone by High-Electric Field Tunnel Ionization at Atmospheric Pressure.

The molecular ion M+· was observed when the liquid sample of butyrophenone was supplied using atmospheric pressure corona discharge (APCD). In contrast, the vapor supply resulted in the formation of the protonated molecule [M+H]+. The mass spectrum obtained with the liquid supply showed two distinctive fragment ions at m/z 105 and 120, resulting from α-cleavage and McLafferty rearrangement (McLR), respectively. The APCD spectrum showed peaks of M+· and the characteristic two fragment ions that were the same as the field ionization mass spectra of butyrophenone as reported by Chait et al. and Beckey et al. The formation of the molecular and fragment ions strongly indicated that high-electric field tunnel ionization (HEFTI) occurs by the HEF strength exceeding 108 V/m at the tip of the corona needle in APCD. The charge and spin density distributions of the molecular and fragment ions were analyzed by quantum chemical calculations using time-dependent density functional theory (TDDFT) and natural bond orbital (NBO) analysis.

Highly Polarization‐Sensitive Solar‐Blind Ultraviolet Photodetection Based on 1D Rb2CuCl3 Microwires

AbstractPolarization‐sensitive solar‐blind ultraviolet (UV) photodetectors are essential in both civilian and military applications. 1D perovskites derivative Rb2CuCl3 holds promise for polarization‐sensitive solar‐blind UV photodetectors due to its wide direct bandgap, anisotropic crystal structure, and long carrier lifetime. However, no studies on the polarization properties of Rb2CuCl3 are reported. Here, the electronic structural anisotropy of Rb2CuCl3 is confirmed by calculating the partial charge density distribution in the ac‐plane and bc‐plane. Then, the Raman‐active modes and corresponding atomic vibration modes are explored within the bc‐plane through joint experimental and theoretical Raman spectroscopy. Besides, angle‐resolved Raman, photoluminescence, and absorption spectroscopy reveal the intriguing anisotropic photoelectric characteristics of Rb2CuCl3 microwires (MWs). By using single Rb2CuCl3 MW as the photoactive layer, a polarization‐sensitive solar‐blind UV photodetector is fabricated, showing high photoresponsivity of 78 mA W−1 and photocurrent anisotropy ratio of ≈1.7 at 265 nm. Importantly, the proposed photodetectors without encapsulation exhibit excellent stability in ambient air, retaining the original photocurrent after two months, showcasing practical applicability. This study underscores the promise of Rb2CuCl3 for high‐performance polarization‐sensitive solar‐blind UV photodetectors, contributing valuable insights into its electronic structure, photoelectric properties, and practical applicability.

First‐Principle Investigation of zb‐TiGe: A Promising Narrow Bandgap Semiconductor

Using first‐principle calculations, a new compound semiconductor based on titanium (Ti) is predicted. It has been observed that Ti when alloyed with germanium (Ge) can crystallize in the zincblende symmetry, and exhibits semiconducting nature with a narrow bandgap. To test the robustness of the semiconducting nature, the structural properties and electronic band structure have been modeled using three different exchange–correlation functionals, namely, local density approximation, generalized gradient approximation, and Perdew‐Burke‐Ernzerhof for solids. With a nominal composition of 1:1, TiGe exhibits a direct bandgap of 0.58 eV at the “X” point of the Brillouin zone. From lattice dynamics, the structural stability of the compound has been established. The new semiconductor is characterized in detail for its electronic band structure, carrier effective mass, charge density distribution, and linear optical properties. Zb‐TiGe exhibits large effective mass for conduction band holes and tentatively becomes a prototype system to study heavy holes resulting in carrier condensation at the bottom of the conduction band. The linear optical properties of the TiGe are found to be suitable for photosensitive devices in the infrared region. In addition, TiGe may find application in deep‐UV and far‐UV regions because of the surface plasmon resonance at 6.4 eV.

A leap forward in the optimization of organic solar cells: DFT-based insights into the design of NDI-based donor-acceptor-donor structures

This study presents the design and analysis of four novel small molecules with a donor-acceptor-donor (D-A-D) architecture, incorporating naphthalene diimide (NDI) as the central electron acceptor core, flanked by different electron-donating units: 4H-dithieno [3,2-b:2′,3′-d]pyrrole (DTP), isomeric 7H-dithieno-[2,3-b:3′,2′-d]pyrrole (iso-DTP), phenothiazine, and diphenylamine. The optical, electronic, and photovoltaic properties of these structures were evaluated using density functional theory (DFT) and time-dependent density functional theory (TD-DFT) at the WB97XD/6-311+G (d,p) theoretical level. The selected calculation method showed excellent agreement with experimental data for the synthesized NDI-C3 molecule, validating the computational approach. Our findings highlight the significant role of electron-donating groups in enhancing photovoltaic properties, including increased open-circuit voltage, improved charge density distribution, and enhanced parameters such as fill factor, radiation lifetime, and light harvesting efficiency compared to the NDI-C3 structure. These promising results underscore the potential of our designed molecules for efficient application in organic solar cells and their significant contribution to the advancement of photovoltaic technology.

Optical and thermoelectric properties of layer structured Ba2XS4 (X = Zr, Hf) for energy harvesting applications

The main objective of this research is to provide a comprehensive insight into the optical and thermoelectric properties of layer structured Ba2XS4(X = Zr, Hf) for energy harvesting applications using Density Functional Theory (DFT) and semiclassical Boltzmann transport theory. There is a good match between the computed lattice parameters and the available experimental data. Both compounds are thermodynamically and mechanically stable and they are soft, ductile, machinable, and elastically anisotropic. The indirect band gaps are found to be 1.03 eV for Ba2ZrS4 and 1.48 eV for Ba2HfS4. Both compounds possess a mixture of ionic and covalent bonding confirmed by charge density distribution and Mulliken bond population analysis. The maximum absorption is in the ultraviolet regions (∼13.6eV) of light spectra. The total thermal conductivity increases with temperature due to increasing trend of electronic thermal conductivity. The total thermal conductivity at 700 K along c-axis is 4.6 (6.1 W/mK) for Ba2ZrS4 (Ba2HfS4). For p-type Ba2ZrS4 (Ba2HfS4), power factor (PF) is about 7 (5.7) mW/mK2, whereas for n-type it is about 4 (3.9) mW/mK2 at 700 K along c-axis. The power factors of the studied compounds are much higher than those of the reported GeTe and SnSe which would create great interest for further study. The predicted ZT values at 700 K for p-type Ba2ZrS4 and Ba2HfS4 are 0.7 and 0.6, respectively. These values may further be improved through reduction of thermal conductivity and tuning ductility employing known suitable strategies such as alloying and nano-structuring. Finally, Ba2ZrS4 and Ba2HfS4 can be considered new eco-friendly alternatives to previously studied toxic lead-based thermoelectric materials. Their unique advantages of high thermodynamic stability, non-toxic nature and high performance make them strong candidate for sustainable energy solutions.

Synthesis, characterization, molecular docking and in vitro antibacterial assessments of anthracene-bis(hydrazine)thiosemicarbazide complexes with Co(II), Ni(II) and Cu(II) ions

As it is essential to develop novel drug candidates that have potent antibacterial as well as antioxidant activities, a new thiosemicarbazide viz N,N'-(2,2′-((9,10,11,12)-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarbonyl)bis(hydrazine-1-carbonothioyl))dibenzamide (H6EDTS) (1) and its Co(II) (2), Ni(II) (3) and Cu(II) (4) complexes have been isolated. The tile compounds were characterized by elemental analyses and spectroscopic measurements. The compounds (2) and (4) were found to be binuclear while compound 4 was a mononuclear one. Spectral FTIR and electronic data showed that H6EDTS coordinating to metal ion as dibasic N2S2O2, NSO and N2O2 chelate in an octahedral arrangement around cobalt(II) ion and square planar one around Ni(II) and Cu(II) ions. The geometry of Cu(II) complex was further proved by its EPR spectrum which showed an intense and broad signal. The TG analyses confirmed the nature of solvent molecules and the thermal stability on complexation. Mulliken and molecular electrostatic potential (MEP) analyses utilized DFT method for the molecular design, optoelectronic properties, HOMO-LUMO energy gaps and, determination of charge density distribution and site of chemical reactivity of the molecule. In addition, all compounds were screened for in vitro antibacterial activity against four pathogenic bacteria and in addition, molecular docking simulations were performed to confirm the interaction. In addition, biological activity is extended to study DNA cleavage, and antioxidant activity viz. Superoxide radicals, and hydroxyl radicals scavenging activities. Furthermore, all compounds and reference drugs (ampicillin) were docked to the target protein using the glide dock XP protocol without performing post-docking minimization.

Adsorption and energy storage characteristics of ionic liquids in porous zeolite-templated carbon materials

The energy storage capacity of supercapacitors is closely related to the capacity of their electrode materials to adsorb electrolytes. Porous zeolite-templated carbon (ZTC) materials are a type of porous carbon material with a well-defined spatial structure and are thus promising electrode materials. This study utilizes molecular dynamics simulations to compare the ion number density and charge density distributions of the [EMI][BF4] ionic liquid for various ZTC materials, while also examining the ion adsorption characteristics for different electrode charges. Parameters such as the degree of confinement (DOC) and the charge compensation per carbon (CCpC) are introduced to represent the ion adsorption and charge storage capacity of the materials, with a higher DOC indicating a greater number of encapsulated ions and a higher CCpC indicating a more efficient charge storage. The findings suggest that materials with a larger pore size tend to exhibit increased ion adsorption. However, many CCpC adsorption sites that can store more charge are then found in positions with a smaller DOC. This work unveils the ion adsorption characteristics of ZTC materials in charged electrode and presents the differential capacitance curves of various materials, thereby providing a theoretical foundation for the utilization of ZTC materials as electrodes in supercapacitors.

Computational study of transition metal coordinated polyaniline: A first principle investigation into tuning the electronic properties of the resulting hybrid material

Tuning the electronic properties of polyaniline remains one of the most important features for the development of advanced materials in electronics. In this contribution, we use density functional theory to investigate the electronic properties of polyaniline when coordinating transition metals (Mn, Fe, Co, Cu, Zn) are embedded in the polymer structure.Importantly, the results reveal that in the presence of transition metal with high electronegativity, the coordinated polyaniline winds up with a decreased gap. Indeed, the band gap for H-PANI decreases from 0.911 eV to 0.513 eV for H-PANI-Mn (lower electronegativity) and to 0.201 eV for H-PANI-Zn (higher electronegativity). This reduction in the energy gap is attributed to enhanced electron delocalization due to increased overlap of electron wavefunctions in the hybrid structure. The results also reveal that the presence of transition metals lead to lower the chemical hardness from 3.252 eV in the case of H-PANI into 0.256 eV for H-PANI-Mn and 0.100 eV for H-PANI-Zn. Additionally, the results from molecular electrostatic potential highlight that PANI-Transition metal sustains more delocalization of charge density distribution compared to H-PANI, leading to molecule polarization which does play a crucial role in various chemical phenomena. These later reveal that the electron density polarization in polyaniline can interestingly be controlled through doping and coordinating the polymer structure with additional transition metals. Therefore, the obtained results might be used in the optimization of electrochemical charge storage in supercapacitors.

Insight into Carrier and Phonon Transports of PbSnS2 Crystals.

The simultaneous optimization of n-type and p-type thermoelectric materials is advantageous to the practical application of the device. As an emerging thermoelectric material, PbSnS2 exhibits highly competitive thermoelectric properties due to its unique carrier and phonon transport characteristics. To promote the utilization of this low-cost thermoelectric material, p-type PbSnS2 crystals are synthesized and optimized through Na doping and Se alloying. The resulting thermoelectric transport properties differ significantly from those reported for n-type crystals, prompting us to compare and analyze both n-type (Cl-doped) and p-type (Na-doped) PbSnS2 crystals from various perspectives. Cl doping is subject to weaker "Fermi pinning" and lower impurity ionization energy compared with Na doping, leading to higher doping efficiency. The different optimal performance directions in n-type and p-type crystals can be attributed to the distinct charge density distributions near the conduction band minimum (CBM) and the valence band maximum (VBM). Additionally, both n-type and p-type crystals exhibit ultralow lattice thermal conductivity due to the low symmetry of their twisted NaCl structure combined with the strong anharmonicity. This comprehensive analysis of PbSnS2 crystals provides a solid foundation for further performance optimization and device assembly, while also sheds light on the investigation of layered thermoelectric materials.