Electron Density Distribution Research Articles

Unveiling the Nature of Chemical Bonds in Real Space.

Recent advent of diverse chemical entities necessitates a re-evaluation of chemical bond concepts, underscoring the importance of experimental evidence. Our prior study introduced a general methodology, termed Core Differential Fourier Synthesis (CDFS), for mapping the distribution of valence electron density (VED) in crystalline substances within real space. In this study, we directly compare the VED distributions obtained through CDFS with those derived from high-accuracy theoretical calculation using long-range corrected density functional theory, which quantitatively reproduces accurate orbital energies. This comparison serves to demonstrate the precision of the CDFS in replicating complex details. The VED patterns observed experimentally exhibited detailed structures and phases of wave functions indicative of sp3 hybrid orbitals, closely aligning with theoretical predictions. This alignment underscores the utility of our approach in gathering quantum chemical data experimentally, a crucial step for discussing the chemical properties, such as reaction mechanisms.

Biaxial strain modulation of NO2 adsorption on χ3 borophene: A first-principles study

Abstract Based on first-principles calculations, the effects of applying biaxial strain to χ3 borophene and the adsorption behavior of NO2 molecule on the surface of χ3 borophene under strain are investigated. Firstly, the pristine borophene exhibits a metallic electronic structure and the thermodynamic stability of χ3 borophene is demonstrated by molecular dynamics simulations. Different adsorption sites and orientations are selected on the χ3 surface, and the optimal adsorption is found to be the S2 conformation, which has an adsorption energy of -1.589 eV. The applied biaxial strain significantly alters the electron density distribution of the χ3 borophene surface, which is predicted to be able to achieve a modification of the adsorption properties for NO2. Finally, we investigate the NO2 adsorption behavior of χ3 borophene surfaces under 1% to 5% biaxial tensile and compressive strains. Biaxial strain is found to enhance the NO2 adsorption capacity of the χ3 borophene surface, and χ3 at 3% biaxial tensile strain has the highest adsorption energy. Therefore, these results show that χ3 borophene can be a candidate material for gas sensors and theoretically guide researchers to develop more effective sensor materials for gas sensing.

Effect of Pyrrolidinedithiocarbamate Ligand on the Luminescence Properties of Heteroligand Samarium and Europium Complexes: Experimental and Theoretical Study.

The photophysical properties of two isostructural heteroligand lanthanide complexes of general formula Ln(pdtc)3(phen) (pdtc = pyrrolidinedithiocarbamate anion, phen = 1,10-phenanthroline), Ln = Sm3+ (1), Eu3+ (2)) were studied in solid state and dichloromethane (DCM) solution. The two lanthanide complexes were investigated by experimental techniques for structural (single-crystal X-ray diffraction analysis of 1, powder XRD, TG-DTA) and spectroscopic [electron paramagnetic resonance (EPR), infrared (IR), ultraviolet-visible (UV-vis), photoluminescence (PL)] characterization. DFT/TDDFT/ωB97xD and multireference SA-CASSCF/NEVPT2 calculations with perturbative spin-orbit coupling corrections were applied to construct the Jablonski energy diagrams and to discuss the excited state energy transfer mechanism with competing excited state processes and possible sensitized mechanism of metal-centered emission. The first excited state (S1) involved in the excited state energy transfer L(antenna)-to-Ln was predicted to have interligand (pdtc-to-phen) charge transfer character in contrast to the previously predicted ligand-to-metal charge transfer character. The theoretical consideration showed similar relaxation paths and luminescence quenching channels and appropriate Donor*(phen)-Acceptor*(Ln3+) energy gap for 1 and 2. The experimental measurements in the solid state, however, showed efficient luminescence and good ability to convert UV to visible light only for the Sm(pdtc)3(phen) complex. The minor emission of 2 was explained by partial reduction of Eu3+, confirmed by EPR and calculated electron density distribution data.

π‐d Conjugated Copper Chloranilate with Distorted Cu‐O4 Site for Efficient Electrocatalytic Ammonia Production

AbstractUnderstanding the relationship between electrocatalytic performance and local structure at the molecular level is of great significance. Herein, a bifunctional electrocatalyst CuCA (CA = chloranilate) is constructed for both nitrogen reduction reaction (NRR) and nitrate reduction reaction (NO3RR). Combined structural analyses using Rietveld refinement, extended X‐ray adsorption fine structure (EXAFS), and pair distribution function (PDF) revealed a significant distortion of the Cu‐O4 structure. Benefitting from the unique local structure, Cu‐CA shows an impressive NH3 yield rate of 286.00 ug h−1 mg−1 (FE = 18.25%, ‐0.85 V vs RHE), 3180.00 ug h−1 mg−1 (FE = 90.3%, ‐0.9 V vs RHE) for NRR and NO3RR, respectively. In contrast, the pyrazine (Pyz) decorated compound Cu‐CA‐Pyz with a less distorted Cu‐O4 structure and fewer active sites show much lower activity. Density functional theory (DFT) calculations shed light on that the distorted nature can effectively regulate the electron density distribution, which can lower the energy barrier of adsorption and activation of the intermediate species, leading to the enhanced activity. These findings may give new insight into the structural‐property relationship and open up opportunities for the exploration of efficient electrocatalysts.

EVOLUTION OF ELECTRONIC PROPERTIES ALONG THE PATH FROM COVALENT TO TETREL BOND IN THE SYNTHESIS OF TETRAPHENYL SUBSTITUTED COMPOUNDS

The evolution of the electronic characteristics of chemical bonds formed and broken along the path of the bimolecular nucleophilic substitution reaction at a tetrahedral central atom, which is the Tt = C, Si, Ge atom, is analyzed. For this purpose, the reaction paths of the step-by-step replacement of the chlorine atom with the phenyl fragment have been modeled, and the energy characteristics of the equilibrium initial, transition and nal states were obtained within the framework of DFT. For different reaction centers, which are atoms of the carbon group (Tt), changes in electron density distributions, shifts in the positions of the extremes of the total static and electrostatic potential for the forming C-Tt and breaking Tt-Cl bonds along the reaction path are compared. Quantitative criteria have been re ned that determine the region of existence of a typical noncovalent tetrel bond Tt...Cl, allowing it to be distinguished from a covalent one. Establishment of the properties of the transition state stabilizing tetrel bond may be useful for monitoring the ef cient synthesis of covalent organic framework precursors.

Effect of CO binding to P450 BM3 F393 mutants on electron density distribution in the heme cofactor

Resonance Raman spectroscopy has been performed on a set of cytochrome P450 BM3 heme domains in which mutation of the highly conserved Phe393 induces significant variation in heme iron reduction potential. In previous work [Chen, Z., Ost, T.W.B., and Schelvis, J.P.M. (2004) Biochemistry 43, 1798–1808], a correlation between heme vinyl conformation and the heme iron reduction potential indicated a steric control by the protein over the distribution of electron density in the reduced heme cofactor. The current study aims to monitor changes in electron density on the ferrous heme cofactor following CO binding. In addition, ferric-NO complexes have been studied to investigate potential changes to the proximal Cys400 thiolate. We find that binding of CO to the ferrous heme domains results in a reorientation of the vinyl groups to a largely out-of-plane conformation, the extent of which correlates with the size of the residue at position 393. We conclude that FeII dπ back bonding to the CO ligand largely takes away the need for conjugation of the vinyl groups with the porphyrin ring to accommodate FeII dπ back bonding to the porphyrin ligand. The ferrous-CO and ferric-NO data are consistent with a small decrease in σ-electron donation from the proximal Cys400 thiolate in the F393A mutant and, to a lesser extent, the F393H mutant, potentially due to a small increase in hydrogen bonding to the proximal ligand. Phe393 seems strategically placed to preserve robust σ-electron donation to the heme iron and to fine-tune its electron density by limiting vinyl group rotation.

Unlocking guanine’s potential: Unveiling electronic transitions and nanoelectronic applications through electric field modulation

Guanines, key players in DNA and RNA, exist as dynamic keto and enol forms, influencing reactivity and potential applications. This study explores the impact of external electric fields on these forms using computational methods in gas and solvent (water) phases. Analyzing the energy gap, dipole moment, enthalpy, and Gibbs free energy revealed distinct responses. The keto form showed a significant decrease in the energy gap in the presence of an electric field, particularly in water, indicating enhanced reactivity. Conversely, the enol form exhibited a stabilizing effect with increasing electric field strength. Thermodynamic properties highlighted solvent-dependent interactions and electric field-induced changes in electron density distribution. The study further investigated guanine’s potential for nanoelectronics by calculating I-V curves, revealing promising characteristics, especially for the keto form in the aqueous phase. Additionally, the analysis of solvation and cohesive energies provided insights into solute–solvent interactions and intrinsic molecular stability. Overall, this research contributes to understanding how guanine responds to electric fields, paving the way for novel guanine-based materials with potential applications in nanoelectronics.

Study of Particle Acceleration Using Fine Structures and Oscillations in Microwaves from the Electron Cyclotron Maser

The accelerated electrons during solar flares produce radio bursts and nonthermal X-ray signatures. The quasi-periodic pulsations (QPPs) and fine structures in spatial–spectral–temporal space in radio bursts depend on the emission mechanism and the local conditions, such as magnetic fields, electron density, and pitch-angle distribution. Radio burst observations with high-frequency time resolution imaging provide excellent diagnostics. In converging magnetic field geometries, the radio bursts can be produced via the electron cyclotron maser (ECM). Recently, using observations made by the Karl G. Jansky Very Large Array (VLA) at 1–2 GHz, Yu et al. reported a discovery of long-lasting auroral-like radio bursts persistent over a sunspot and interpreted them as ECM-generated emission. Here we investigate the detailed second and subsecond temporal variability of this continuous ECM source. We study the association of 5 s period QPPs with a concurrent GOES C1.5-class flare, utilizing VLA’s imaging spectroscopy capability with an extremely high temporal resolution (50 ms). We use the density and magnetic field extrapolation model to constrain the ECM emission to the second harmonic O-mode. Using the delay of QPPs from X-ray emission times, combined with X-ray spectroscopy and magnetic extrapolation, we constrain the energies and pitch angles of the ECM-emitting electrons to ≈4–8 keV and >26°. Our analysis shows that the loss-cone diffusion continuously fuels the ECM via Coulomb collisions and magnetic turbulence between a length scale of 5 and 100 Mm. We conclude that the QPP occurs via the Lotka–Volterra system, where the electrons from solar flares saturate the continuously operating ECM and cause temporary oscillations.

Influence of the Hubbard U Correction on the Electronic Properties and Chemical Bands of the Cubic (Pm3¯m) Phase of SrTiO3 Using GGA/PBE and LDA/CA-PZ Approximations.

By using DFT simulations employing the GGA/PBE and LDA/CA-PZ approximations, the effects of the Hubbard U correction on the crystal structure, electronic properties, and chemical bands of the cubic phase (Pm3¯m) of STO were investigated. Our findings showed that the cubic phase (Pm3¯m) STO's band gaps and lattice parameters/volume are in reasonably good accordance with the experimental data, supporting the accuracy of our model. By applying the DFT + U method, we were able to obtain band gaps that were in reasonably good agreement with the most widely used experimental band gaps of the cubic (Pm3¯m) phase of STO, which are 3.20 eV, 3.24 eV, and 3.25 eV. This proves that the Hubbard U correction can overcome the underestimation of the band gaps induced by both GGA/PBE and LDA/CA-PZ approximations. On the other hand, the Sr-O and Ti-O bindings appear predominantly ionic and covalent, respectively, based on the effective valence charges, electron density distribution, and partial density of states analyses. In an attempt to enhance the performance of STO for new applications, these results might also be utilized as theoretical guidance, benefitting from our precise predicted values of the gap energies of the cubic phase (Pm3¯m).

The Synthesis, Structural Characterization, and DFT Calculation of a New Binuclear Gd(III) Complex with 4-Aacetylphenoxyacetic Acid and 1,10-Phenanthroline Ligands and Its Roles in Catalytic Activity.

A new binuclear Gd(III) complex, [Gd2(L)6(Phen)2]·4H2O, was synthesized via the reaction of gadolinium(III) nitrate hexahydrate, 4-acetylphenoxyacetic acid (HL), NaOH, and 1,10-phenanthroline (Phen) in a solution of water-ethanol (v:v = 1:1). The Gd(III) complex was characterized using IR, UV-vis, TG-DSC, fluorescence, and single-crystal X-ray diffraction analyses. The results showed that the Gd(III) complex crystallizes in the triclinic system, space group P-1, and each Gd(III) ion was coordinated with two nitrogen atoms (N1, N2, or N1a, and N2a) from two Phen ligands and seven oxygen atoms (O1, O2, O7a, O9, O8, O8a, O10a, or O1a, O2a, O7, O8, O8a, O9a, and O10) from six L ligands, respectively, forming a nine-coordinated coordination mode. The Gd(III) complex molecules formed a one-dimensional chained and three-dimensional network structure via benzenering π-π stacking. The Hirschfeld surface analysis and the calculations of the electron density distributions of the frontier molecular orbitals of the Gd(III) complex were performed. The catalytic activities of the photocatalytic CO2 reduction and benzyl alcohol oxidation using the Gd(III) complex as a catalyst were performed. The results of the photocatalytic CO2 reduction showed that the yield and the selectivity of CO reached 41.5 μmol/g and more than 99% after four hours, respectively. The results of the benzyl alcohol oxidation showed that the yield of benzaldehyde was 45.7% at 120 °C with THF as the solvent under 0.5 MPa O2 within 2 h.

Giant ab‐Plane Birefringence in Quasi‐1D Fibrous Red Phosphorus

AbstractQuasi‐one‐dimensional (quasi‐1D) van der Waals crystal fibrous red phosphorus (RP) exhibits pronounced in‐plane optical anisotropy, positioning it as a potential candidate for polarization‐related micro‐nano devices. Unfortunately, a comprehensive investigation into the complex refractive index of fibrous RP and the structure–activity relationship connecting the distinctive quasi‐1D structure with optical anisotropy is currently deficient. Herein, we have collectively determined the complex refractive index of the fibrous RP flakes within the ab‐plane through Kramers–Kronig (KK) analysis and theoretical calculation. Notably, the maximum birefringence of fibrous RP reaches 0.642@475 nm with an absolute extinction coefficient of only 0.08, superior to the reported traditional optical crystals and the emerging low‐dimensional materials as well. The remarkable birefringence can be attributed to the synergistic influence of the large electronic dipole polarizability, anisotropic electron density distribution and the distortion of stereochemically active lone pair (SCALP). This work demonstrates the potential of fibrous RP for polarization‐sensitive devices, illuminating possibilities to exploit novel giant birefringent crystals based on the structure–activity relationship.

Imination of Sterically Unshielded o‐Quinones in the Coordination Sphere of Zinc (II)

Abstracto‐Iminoquinones bearing unshielded chelating OCCN(R) site were synthesized in high yields in the zinc coordination sphere as the neutral complexes. The stability of one‐electron‐reduced forms of these o‐iminoquinones and the distribution of the unpaired electron density in the corresponding radical anion species were studied using cyclic voltammetry and EPR spectroscopy methods

Fe-N co-doped carbon nanofibers with Fe3C decoration for water activation induced oxygen reduction reaction

Abstract Proton activity at the electrified interface is central to the kinetics of proton-coupled electron transfer (PCET) reactions in electrocatalytic oxygen reduction reaction (ORR). Here, we construct an efficient Fe3C water activation site in Fe-N co-doped carbon nanofibers (Fe3C-Fe1/CNT) using an electrospinning-pyrolysis-etching strategy to improve interfacial hydrogen bonding interactions with oxygen intermediates during ORR. In situ Fourier transform infrared spectroscopy and density functional theory studies identified delocalized electrons as key to water activation kinetics. Specifically, the strong electronic perturbation of the Fe–N4 sites by Fe3C disrupts the symmetric electron density distribution, allowing more free electrons to activate the dissociation of interfacial water, thereby promoting hydrogen bond formation. This process ultimately controls the PCET kinetics for enhanced ORR. The Fe3C-Fe1/CNT catalyst demonstrates a half-wave potential of 0.83 V in acidic media and 0.91 V in alkaline media, along with strong performance in H2-O2 fuel cells and Al-air batteries.

Space-resolved electron density and temperature evaluation by x-ray pinhole camera method in an ECR plasma

X-ray emission characterization provides valuable insights about electron cyclotron resonance (ECR) plasmas. In principle, space-resolved spectroscopic techniques can be used to reveal spatial distributions of electron density and temperature. In the PANDORA (Plasma for Astrophysics, Nuclear Decay Observation, and Radiation for Archaeometry) project framework, and within the collaboration between the Atomki and INFN-LNS laboratories, we developed a high-resolution full-field x-ray pinhole setup. This setup incorporates advanced analysis techniques for single photon counted imaging in high dynamical range mode, enabling x-ray imaging and space-resolved spectroscopy at high spatial and energy resolution (560 μm and 242 eV @ 8.1 keV, respectively). Here, we introduce an innovative technique for quantitatively evaluating the local electron density and temperature of plasma, as the first application of such a method in an ECR setup. Specifically, we examine an argon plasma heated by 200 W microwave power at 14 GHz. Our analysis includes a retrospective comparison with past x-ray data collected from other ECR ion source setups. Our findings clearly reveal the formation of a plasmoid–halo structure within the plasma chamber, characterized by a dense and hot plasma almost totally enclosed inside the ECR magnetic iso-surface (the plasmoid). This plasmoid exhibits nearly uniform distribution of electron density and temperature, with only gentle gradients of both the parameters toward its edges. Inside the halo, x-ray emission is minimal or even negligible. Notably, cusp structures correspond to magnetic branches where deconfined electrons impinge upon the plasma chamber walls and endplates. The average values of temperature and density measured inside the plasmoid are 12.44±1.84 keV and (1.66±0.15)×1017 m−3, respectively.

DFT, Molecular Docking, Bioactivity and ADME Analyses of Vic-dioxim Ligand Containing Hydrazone Group and its Zn(II) Complex.

Cancer is one of the diseases affecting a large population worldwide and resulting in death. Finding new anti-cancer drugs that are target-focused and have low toxicity is of great importance. This study aimed to investigate the effects of vic-dioxime derivatives carrying hydrazone group and its Zn(II) complex on cancer using molecular docking, bioactivity and quantum chemical calculations. Molecular docking studies were performed on epidermal growth factor receptor and vascular endothelial growth factor receptor 2 target proteins. Furthermore, molecular geometry was performed, and the frontier molecular orbitals, Mulliken charges and molecular electron density distribution were evaluated using density functional theory. Also, the bioactivity parameters of the compounds were evaluated, and ADME analysis was performed using web-based tools. Higher binding affinity was observed for Zn(II) complex with target proteins vascular endothelial growth factor receptor 2 and against epidermal growth factor receptor when compared with LH2. Only the Zn(II) complex against the epidermal growth factor receptor had ligand efficiency and fit quality in the valid range. Furthermore, LH2 has the most potent electrophilic ability (acceptor) among other compounds. Moreover, both LH2 and Zn(II) complexes strongly satisfy Lipinski's rule of five. In conclusion, these novel compounds, especially Zn(II) complex, can be new candidates for anticancer drug development studies which are target-focused and have low toxicity.

Vibrational Self-Consistent Field (VSCF) and Post-VSCF Method Calculations Combined with the Reference Interaction Site Model Self-Consistent Field Method Coupled with the Constrained Spatial Electron Density Distribution: Applications to NaHCOO in Aqueous Phase.

Investigating vibrational behavior in solution is crucial for understanding molecular dynamics within a solvent environment. Notably, the analysis of Raman spectra for molecules in solution is important owing to its ability to unveil intricate solute-solvent interactions. Previous studies have effectively employed frequency calculations utilizing the reference interaction site model self-consistent field method in conjunction with constrained spatial electron density distribution (RISM-SCF-cSED) to understand molecular vibrations in solution, primarily focusing on fundamental vibrational modes. However, the oversight of overtones and combination tones in these studies prompted us to combine the vibrational self-consistent field (VSCF) and vibrational second-order Mo̷ller-Plesset perturbation (VMP2) methods with RISM-SCF-cSED to address these aspects theoretically. Illustrating the efficacy of this integrated approach, we computed the Raman spectra of sodium formate (NaHCOO) in water, revealing the necessity of accounting for molecular anharmonicity in solution vibrational analysis. Our findings underscore the potency of VSCF and VMP2 in conjunction with RISM-SCF-cSED as a robust theoretical framework for such calculations.

Application of generalized aurora computed tomography to the EISCAT_3D project

Abstract. EISCAT_3D is a project to build a multi-site phased-array incoherent scatter radar system in northern Fenno-Scandinavia. We demonstrate via numerical simulation how useful monochromatic images taken by a multi-point imager network are for auroral research in the EISCAT_3D project. We apply the generalized aurora computed tomography (G-ACT) method to modelled observational data from real instruments, such as the Auroral Large Imaging System (ALIS) and the EISCAT_3D radar. G-ACT is a method for reconstructing the three-dimensional (3D) distribution of auroral emissions and ionospheric electron density (corresponding to the horizontal two-dimensional (2D) distribution of energy spectra of precipitating electrons) from multi-instrument data. It is assumed that the EISCAT_3D radar scans an area of 0.8° in geographic latitude and 3° in longitude at an altitude of 130 km with 10 × 10 beams from the radar core site at Skibotn (69.35° N, 20.37° E). Two neighboring discrete arcs are assumed to appear in the observation region of the EISCAT_3D radar. The reconstruction results from G-ACT are compared with those from the normal ACT as well as the ionospheric electron density from the radar. It is found that G-ACT can interpolate the ionospheric electron density at a much higher spatial resolution than that observed by the EISCAT_3D radar. Furthermore, the multiple arcs reconstructed by G-ACT are more precise than those by ACT. In particular, underestimation of the ionospheric electron density and precipitating electrons' energy fluxes inside the arcs is significantly improved by G-ACT including the EISCAT_3D data. Even when the ACT reconstruction is difficult due to the unsuitable locations of the imager sites relative to the discrete arcs and/or a small number of available images, G-ACT allows us to obtain better reconstruction results.

Selective deposition and confined pyrolysis towards carbon nanorings for highly surface-dominated and durable sodium storage

Implementing a highly surface-dominated Na+ adsorption mechanism over carbon-based anodes is promising for high-rate and durable sodium storage. However, the nanostructure/microenvironment of most existing carbon materials still fails to sufficiently unlock the mechanism. Herein, we initially report selective deposition and confined pyrolysis strategies to engineer double-concave carbon nanorings (CNRs) with a precisely-controlled microenvironment to tackle this issue. The present strategies simultaneously endow the obtained CNRs with ultrahigh N-doping (N-CNRs, up to 18.6 at% even at 800 °C), rich defects, and thin-wall porous nanostructure. Such N-CNRs largely shorten the route distances for ion diffusion and provide enriched active sites, enabling highly surface-dominated sodium storage. Consequently, a high reversible capacity (387 mA h g−1 at 0.1 A g−1), outstanding rate capability (180 mA h g−1 even at 10.0 A g−1), with extra-long cycle life (over 10 000 cycles at 5.0 A g−1, 0.35 ‱ capacity decay per cycle) is achieved. In addition, the density functional theory calculations further illustrate that high N-doping carbon vacancy defects can effectively optimize electron density distribution, thereby significantly enhancing the capacity for sodium adsorption. This work opens a new avenue to microenvironment-engineered novel carbon nanostructures for highly surface-dominated sodium storage.

Quantum computational, solvation and in-silico biological studies of a potential anti-cancer thiophene derivative

Heterocyclic molecules display a wide spectrum of properties that span both material and biological domains. Material properties stem from their interactions in the bulk, where a large number of molecules of the same type get together resulting in an enhancement of properties. However, biological properties emanate from the interaction of a single or a few molecules with a biologically functional macromolecule. Computational tools offer a particularly useful way of theoretically studying molecules to arrive at a conclusion regarding such properties, even though they may vary when experimentally evaluated. This study concerns itself with the theoretical investigation comprising density functional theory calculations, topological analyses and in-silico biological evaluation of a thiophene compound, i.e. the title compound. Density functional theory was used to compute properties of the title molecule and their variations in unsolvated and solvated phases using Gaussian 09. The molecule in solvent phases encompassing organic polar protic, organic polar aprotic and inorganic polar protic nature have been subjected to theoretical investigations. The suitability of the molecule for deployment as a modern optical material is examined with positive results. Topological characteristics of the molecule were evaluated using Multiwfn 3.8 to examine electron density distribution and the possible resulting covalent, non-covalent and weak interactions because of such distribution. The potency of the molecule towards brain cancer was evaluated by molecular docking with Auto Dock Tools against two brain cancer protein targets 6ETJ and 6YPE with a good docking score of −6.63 and −6.21 kcal mol−1 respectively and the resulting interactions visualized and its pharmacokinetic properties obtained using online tools.

First-principles investigation of the thermal properties of XO (X=Be, Mg and Sr) nanosheet

The electronic structures and thermal properties of hexagonal XO ([Formula: see text], Mg and Sr) nanosheets are studied within the density functional theory. The thermal properties are computed using the specified structural parameters of the electronic properties. Thermal properties including entropy, enthalpy, free energy and heat capacity for XO nanosheets are reported. It is found that BeO is an insulator, whereas MgO and SrO are semiconductors based on the energy gap value within GGA and HSE06. The electronegativity and bonding nature of XO nanosheets differ, resulting in considerable variations in thermodynamic parameters that follow a similar pattern as a function of temperature. Enthalpy and entropy increase with temperature whereas free energy falls, owing to a change in the binary oxide internal energy of the system and the electron density distribution. Thermal energy absorbed by the lattices grows with increasing temperature to the point at which all of their modes are activated and the systems start to display unharmonicity deviating from a linear dependence. Variable parameter ranges for XO nanosheets are useful in the development of thermoelectric nanodevices.