Changes In Electronic Structure Research Articles

Improved Urea Oxidation Performance via Interface Electron Redistributions of the NiFe(OH)x/MnO2/NF p-p Heterojunction.

The development of highly efficient urea oxidation reaction (UOR) electrocatalysts is the key to simultaneously achieving green hydrogen production and the treatment of urea-containing wastewater. Ni-based electrocatalysts are expected to replace precious metal catalysts for UOR because of their high activity and low cost. However, the construction of Ni-based electrocatalysts that can synergistically enhance UOR still needs further in-depth study. In this study, highly active electrocatalysts of NiFe(OH)x/MnO2 p-p heterostructures are constructed on nickelfoam (NF) by electrodeposition (NiFe(OH)x/MnO2/NF), illustrating the effect of electronic structure changes at heterogeneous interfaces on UOR and revealing the catalytic mechanism of UOR. The NiFe(OH)x/MnO2/NF only needs 1.364V (vs Reversible Hydrogen Electrode, RHE) to reach 10mA cm-2 for UOR. Structural characterizations and theoretical calculations indicate that energy gap leads to directed charge transfer and redistribution at the heterojunction interface, forming electron-rich (MnO2) and electron-poor (NiFe(OH)x) regions. This enhances the catalyst's adsorption of urea and reaction intermediates, reduces thermodynamic barriers during the UOR process, promotes the formation of Ni3+ phases at lower potentials, and thus improves UOR performance. This work provides a new idea for the development of Ni-based high-efficiency UOR electrocatalysts.

Primary processes of the archetypal model complex azido(porphinato)iron(III) from ultrafast vibrational-electronic spectroscopy.

Azidoiron complexes serve as valuable photochemical precursors for catalytically active species containing high-valent iron. In bioinorganic chemistry, azido(tetraphenylporphinato)iron(III), i.e., [FeIII(tpp)(N3)] with tpp = 5, 10, 15, 20-tetraphenylporphyrin-21, 23-diido, constitutes the archetypal model system that was used to access for the first time the terminal nitridoiron core, FeV ≡ N, in the biomimetic redox-non-innocent ligand environment. So far, the light-induced dynamics leading to the oxidation of the metal and the release of dinitrogen from the N3-ligand have only been studied for precursors featuring redox-innocent auxiliary ligands that simplify the electronic structure change accompanying the photo-transformation. Here, we monitored the primary events of the above paradigmatic complex, following its optical excitation in the ultraviolet-to-visible spectral range using femtosecond spectroscopy with probing in both the UV-vis and mid-infrared regions. Following ultrafast Soret-excitation at 400nm, the complex relaxes to the lowest excited sextet state by a first internal conversion in less than 200fs. The excited state then undergoes vibrational relaxation on a time scale of roughly 2ps before internally converting yet again to recover the sextet electronic ground state within 19.5ps. Spectroscopic evidence is obtained neither for a transient occupation of the energetically lowest metal-centered state, 41A1, nor for vibrational relaxation in the ground-state. The primary processes seen here are thus in contrast to those previously derived from ultrafast UV-pump/vis-probe and UV-pump/XANES-probe spectroscopies for the halide congener [FeIII(tpp)(Cl)]. Any photochemical transformation of the complex arises from two-photon-induced dynamics.

Constant potential energetics of metallic and semiconducting electrodes: A benchmark study on 2D materials.

Grand-canonical (GC) constant-potential methods within an implicit solvent environment provide a general approach to compute the potential-dependent energetics at electrified solid-liquid interfaces with first-principles density-functional theory. Here, we use a mindfully chosen set of 27 isostructural 2D metal halides MX2 to analyze the variation of this energetics when the electronic structure changes from metallic to semiconducting and insulating state. Apart from expectable changes due to the opening up of the electronic bandgap, the calculations also show an increasing sensitivity to the numerical Brillouin zone integration and electronic smearing, which imposes computational burdens in practice. We rationalize these findings within the picture of the total interfacial capacitance arising from a series connection of the electrochemical double-layer capacitance and the so-called quantum capacitance resulting from the filling of electronic states inside the electrode. For metals, the electrochemical double-layer capacitance dominates at all potentials, and the entire potential drop takes place in the electrolyte. For semiconductors, the potential drop occurs instead fully or partially inside the electrode at potentials within or just outside the bandgap. For 2D semiconductors, the increased sensitivity to numerical parameters then results from the concomitantly increased contribution of the quantum capacitance that is harder to converge. Fortunately, this understanding motivates a simple extension of the CHE + DL approximation for metals, which provides the approximate GC energetics of 2D semiconductors using only quantities that can be obtained from computationally undemanding calculations at the point of zero charge and a generic double-layer capacitance.

Phase Transition Control in Molecular Solids via Complementarity of Hydrogen-Bond Strength.

Phase transitions in molecular solids involve synergistic changes in chemical and electronic structures, leading to diversification in physical and chemical properties. Despite the pivotal role of hydrogen bonds (H-bonds) in many phase-transition materials, it is rare and challenging to chemically regulate the dynamics and to elucidate the structure-property relationship. Here, four high-spin CoIIcom-pounds were isolated and systematically investigated by modifying the ligand terminal groups (X = S, Se) and substituents (Y = Cl, Br).S-ClandSe-Brundergo a reversible structural phase transition near room temperature, triggering the rotation of 15-crown-5 guests and the swing between syn- and anti-conformation of NCX-ligands, accompanied by switchable magnetism. Conversely,S-BrandSe-Clretain stability in ordered and disordered phases, respectively. H-bonds geometric analysis andab initiocalculations reveal that the electronegativity of X and Y affects the strength of NY-ap-H···X interactions. Entropy-driven structural phase transitions occur when the H-bond strength is appropriate; otherwise, the phase stays unchanged if it is too strong or weak. This work highlights a phase transition driven by H-bond strength complementarity - pairing strong acceptor with weak donor andvice versa, which offers a straightforward and effective approach for designing phase-transition molecular solids from a chemical perspective.

Probing Electronic Structure Changes in Cobalt Oxalate Anode for Lithium‐Ion Batteries

AbstractTransition metal‐based materials exhibit a broad range of catalytic activities in numerous electrochemical processes. Their displayed catalytic functions rely essentially on their distinctive electronic structures, changes of which play pivotal roles in dictating reaction dynamics within many electrochemical devices. Nevertheless, accurately probing electronic structure changes, especially in real‐time, of active materials remains a formidable challenge. In this work, a viable approach to achieve it within a CoC2O4/Li model system by employing a combined microscopic is demonstrated, spectroscopic analysis, plus a unique operando magnetometry technique. The findings reveal that upon completion of the conventional conversion of CoC2O4, a surface‐dominated capacitance emerges at the Co/Li2C2O4 interface owing to the injection of spin‐polarized electrons. Subsequently, the decomposition of Li2C2O4 proceeds through the releasing of the spin‐polarized electrons from Co, which, therefore serve as a catalyst leading to further discharge products. Such real‐time monitoring of electron transfer is realized by in situ monitoring electronic structure changes of Co, manifested by its intriguing magnetization alterations during the process. This work highlights a novel characterization tool that provides a solid explanation for the commonly observed large capacities in this type of materials and sheds light on design rules and selection guidance of materials for high‐performance electrochemical energy storage systems.

Flavonoid Oxidation Potentials and Antioxidant Activities-Theoretical Models Based on Oxidation Mechanisms and Related Changes in Electronic Structure.

Herein, I will review our efforts to develop a comprehensive and robust model for the estimation of the first oxidation potential, Ep1, and antioxidant activity, AA, of flavonoids that would, besides enabling fast and cheap prediction of Ep1 and AA for a flavonoid of interest, help us explain the relationship between Ep1, AA and electronic structure. The model development went forward with enlarging the set of flavonoids and, that way, we had to learn how to deal with the structural peculiarities of some of the 35 flavonoids from the final calibration set, for which the Ep1 measurements were all made in our laboratory. The developed models were simple quadratic models based either on atomic spin densities or differences in the atomic charges of the species involved in any of the three main oxidation mechanisms. The best model takes into account all three mechanisms of oxidation, single electron transfer-proton transfer (SET-PT), sequential proton loss electron transfer (SPLET) and hydrogen atom transfer (HAT), yielding excellent statistics (R2 = 0.970, S.E. = 0.043).

Photophysical Studies of a Zr(IV) Complex with Two Pyrrolide-Based Tetradentate Schiff Base Ligands.

The reaction of two equivalents of N,N'-bis(2-pyrrolylmethylidene)-1,2-phenylenediamine (H2bppda) with tetrabenzylzirconium provided the air- and moisture-stable eight-coordinate complex Zr(bppda)2. Temperature-dependent steady-state and time-resolved emission spectroscopy established weak photoluminescence (ΦPL = 0.4% at 293 K) by a combination of prompt fluorescence and thermally activated delayed fluorescence (TADF) upon visible light excitation at and around room temperature. TADF emission is strongly quenched by 3O2 and shows highly temperature-sensitive emission lifetimes of hundreds of microseconds. The lifetime of the lowest energy singlet excited state, S1, was established by transient absorption spectroscopy and shows rapid deactivation (τ = 142 ps) by prompt fluorescence and intersystem crossing to the triplet state, T1. Time-dependent density functional theory (TD-DFT) calculations predict moderate ligand-to-metal charge transfer (LMCT) contributions of 25-30% for the S1 and T1 states. A comparison of Zr(bppda)2 to related zirconium pyridine dipyrrolide complexes, Zr(PDP)2, revealed important electronic structure changes due to the eight-coordinate ligand environment in Zr(bppda)2, which were correlated to differences in the photophysical properties between the two compound classes.

Enhanced thermoelectric figure of merit in graphene nanoribbons by creating a distortion and transition-metal doping

Thermoelectric (TE) materials have the exceptional ability to directly convert waste heat into electricity and theoretical studies-based guidance is an effective way to investigate high-performance nanostructured TE materials throughout a range of temperatures. Herein, we studied the influence of distortion and transition metal (TM) atoms (V, Cr, Co and Pt) on the electronic and TE properties of armchair graphene nanoribbons (AGNRs) at various temperatures. The results showed that TM-doping and distortion might significantly alter the electronic structure of AGNRs. The band gap and valence band convergence are reduced as a result of the synergistic effect. A higher TE figure of merit results from a combination of decreased heat conductivity and increased electrical conductivity brought about by the electronic structural change. This study proposes that by doping and distortion-induced TE characteristics engineering of AGNR, high-performance nanostructured TE materials may be produced that have a wide range of TE applications.

Effects of Static Electric Fields on the Excitations of Silver Nanowire Dimers.

We theoretically studied the introduction of static electric fields to Ag10 nanowire dimer systems, including the effects of this field on optical absorption characteristics and the orbitals responsible for these excitations. Linear-response time-dependent density functional theory computations were performed on three distinct dimer systems: end-to-end, parallel, and 90° angle dimer systems separated by a closest interparticle distance of 7.0 Å. The calculations were performed in the presence of a 0.1 V/Å electric field strength applied in the z and y directions. The orientation of the dimer system and the direction of the applied static electric field each play a significant role in the resulting absorption spectra and the electronic structure of the nanowires. As a result, a dimer system can exhibit a blue shift for the longitudinal excitation and a red shift for the transverse excitation in the presence of one direction of the static electric field but not for the other direction. Notably, the electron density shifts from one nanowire to the other in the presence of the static electric field. Changes in optical characteristics and electronic structure suggest that the usage of a static electric field with a particular spatial configuration of nanowires provides a way to tune the optical properties of the system.

Solar-photocatalytic treatment of industrial wastewater using mechanically doped CNS-TiO2 and synergistic TiO2 incorporation: A promising cost-effective approach for industrial wastewater treatment

TiO2 alone demonstrated limited efficiency in degrading industrial wastewater. This study aims to the effectiveness of CNS-doped TiO2 nanoparticles for the degradation of anionic dyes, cationic dyes, and industrial wastewater. For the first time, mechanical milling is employed to synthesize CNS-doped TiO2 nanoparticles using thiourea as a precursor. This results in lattice strains and concomitant crystal and electronic structure changes. We note that these lead to increased photocatalytic activity. Mechanical milling creates a new phase known as brookite, which further improves photocatalytic efficiency through synergistic effects. The physicochemical properties and photocatalytic performance of CNS-TiO2 are evaluated and compared with mspd-TiO2 and commercially available Degussa P-25 TiO2. In photocatalytic degradation tests, remarkably, CNS-TiO2 exhibited beter degradation efficiency for anionic dyes (MO - 65 ± 3 % in 120 min; CR - 100 % in 30 min), cationic dyes (MB - 100 % in 30 min; Rh B 100 % in 120 min) and industrial wastewater (∼100 % in 120 min). The treated wastewater TDS (56 ± 2 ppm), TSS (0.16 g/L), CHNS, and COD (190 ± 10 mg/L) results are closer to drinking water quality. The reusability test revealed lower activity in the mspd-TiO2 and CNS-TiO2 attributed to particle aggregation, the loss of activation sites, and mass loss. This study demonstrates CNS-TiO2 enhanced photocatalytic properties and cost-effectiveness making them highly promising for treating any industrial effluents containing dyes.

High piezoelectric coefficients and rich phase transitions in ternary TlXY (X = S, Se; Y = Cl, Br, I) monolayers

In this work, we investigated the structural, electronic, optical, and piezoelectric properties of TlXY (X = S, Se; Y = Cl, Br, I) monolayers using the first-principles calculations. Five types of TlXY monolayers are structurally stable. The band gap, which ranges from 0.371-2.196 eV, is direct for most TlXY and indirect for TlSeBr. With adequate flexibility, the in-plane and out-of-plane piezoelectric coefficients, d11 and d31, of TlXY can approach 77.05-90.55 pm/V and 0.70-1.08 pm/V, respectively, which is larger than those of reported 2D materials. Strain can cause a direct-to-indirect band gap transition or even a topological phase transition. Furthermore, TlSeBr and TlSI can undergo structural phase transitions, resulting in dramatic changes in electronic structure and optical absorption. Our results suggest 2D TlXY as a series of promising materials for optoelectronic and piezoelectric applications.

Computational investigation of structural, electronic, and spectroscopic properties of Ni and Zn metalloporphyrins with varying anchoring groups.

Porphyrins are prime candidates for a host of molecular electronics applications. Understanding the electronic structure and the role of anchoring groups on porphyrins is a prerequisite for researchers to comprehend their role in molecular devices at the molecular junction interface. Here, we use the density functional theory approach to investigate the influence of anchoring groups on Ni and Zn diphenylporphyrin molecules. The changes in geometry, electronic structure, and electronic descriptors were evaluated. There are minimal changes observed in geometry when changing the metal from Ni to Zn and the anchoring group. However, we find that the distribution of electron density changes when changing the anchoring group in the highest occupied and lowest unoccupied molecular orbitals. This has a direct effect on electronic descriptors such as global hardness, softness, and electrophilicity. Additionally, the optical spectra of both Ni and Zn diphenylporphyrin molecules exhibit either blue or red shifts when changing the anchoring group. These results indicate the importance of the anchoring group on the electronic structure and optical properties of porphyrin molecules.

Local strain induced structural inhomogeneity in Fe thin films on Cu(001)

We investigate atomic-scale surface structures of 7 monolayer Fe thin films on a Cu(001) substrate by scanning tunneling microscopy. Near the step edges, the epitaxial fcc(001) lattice is stabilized on the upper terrace. In contrast, on the lower terrace, the bulk stable bcc(110) lattice and several surface reconstructions with high-density adsorbates are observed. The changes of electronic structures on the latter region from fcc Fe to bcc Fe is verified by spectroscopic measurements after the desorption of adsorbates, suggesting the local strain effect as the dominant origin of observed structural inhomogeneity.

The Spin-Orbit Effect on the Electronic Structures, Refractive Indices, and Birefringence of X2PO4I (X = Pb, Sn, Ba and Sr): A First-Principles Investigation.

Introducing post-transition metal cations is an excellent strategy for enhancing optical properties. This paper focuses on four isomers, namely the X2PO4I (X = Pb, Sn, Ba, and Sr) series. For the first time, the paper's attention is paid to the changes in electronic structure, as well as refractive indices and birefringence, with and without the inclusion of spin-orbit effects in this series. The first-principles results show that spin-orbit effects of the 5p and 6p states found in these compounds lead to splitting of the bands, narrowing of the band gap, enhancement of the lone-pair stereochemistry, and enhancement of the refractive indices and birefringence. Moreover, a comparison of the lone-pair electron phosphates, X2PO4I (X = Pb and Sn), and the isomeric alkaline earth metal phosphates, X2PO4I (X = Ba and Sr), reveals that changes in the band structure have a greater effect on the enhancement of the birefringence than the slight enhancement of the lone-pair stereochemical activity. This study has important implications for a deeper understanding of the optical properties of crystals and the design of novel optical materials.

Pressure-Driven Energy Band Gap Narrowing of λ-N2

Probing the energy band gap of solid nitrogen at high pressures is of importance for understanding pressure-driven changes in electronic structures and insulator-to-metal transitions under high pressure. The λ-N2 formed by cold compression is known to be the most stable one in all solid nitrogen phases observed so far. By optimizing the optical system, we successfully measured the high-pressure absorption spectra of λ-N2 covering the polymeric-nitrogen synthetic pressures (124 GPa–165 GPa). The measured optical band gap decreases with increasing pressure, from 2.23 eV at 124 GPa to 1.55 eV at 165 GPa, with a negative pressure coefficient of −18.4 meV/GPa, which is consistent with the result from our ab initio total-energy calculations (−22.6 meV/GPa). The extrapolative metallization pressure for the λ-N2 is around 288(18) GPa, which is close to the metallization pressure (280 GPa) for the η-N2 expected by previous absorption edge and direct electrical measurements. Our results provide a direct spectroscopic evidence for the pressure-driven band gap narrowing of solid nitrogen.

A hybrid density functional study of tensile-induced changes in phonon dispersion, electronic structure and optical absorption of bilayer BN for optoelectronic applications

The electronic, phonon dispersion and optical properties of bilayer BN have been investigated with density functional theory (DFT) calculations. Interestingly, applying the biaxial strain of 4% converts the indirect band gap of bilayer BN to a direct band gap. We show that the interaction between the BN layers results in the removal of two-fold degeneracy and separation of ZA and ZO phonon modes near the Γ point. Across the entire range of applied biaxial tensile strains, the bilayer BN exhibits a dynamically stable behavior. The phonon bandgap of bilayer BN decreases under tensile strain. The bilayer BN has strong adsorption in the UV region and the optical absorption peaks are red-shifted by applying the tensile strain. These findings are essential for the strain engineering of bilayer BN and future fabrication of flexible electronic and optoelectronic devices.

Structural Changes in the Carbon Sphere of a Dirhodium Complex Induced by Redox or Deprotonation Reactions.

A carbon-rich molecule is synthesized, which mainly contains conjugated sp2 and sp hybridized carbon centers. Alkenyl and alkynyl binding sites are arranged such that this compound serves as ligand to a binuclear metal unit with a RhI─RhI bond. Furthermore, CH units are placed in proximity to the metal centers. The dicationic complex [Rh2(bipy)2{Ph2Ptrop(C≡CCy)2}]2+(OTf-)2 allows to study possible responses of the carbon-framework to redox reactions as well as deprotonation reactions. All products are, whenever possible, characterized by X-ray diffraction (XRD) methods, NMR and EPR spectroscopy as well as electrochemical methods. It is shown that the carbon skeleton of the ligand framework undergoes C─C bond rearrangement reactions of remarkable diversity. In combination with DFT (density functional theory) studies, these results allow to gain insight into the electronic structure changes caused by metal sites in a carbon-rich environment, which may be of relevance for the properties of metal particles on carbon support materials when they are exposed to hydrogen, electrons, or protons.

Pressure Driven Fractionalization of Ionic Spins Results in Cupratelike High-T_{c} Superconductivity in La_{3}Ni_{2}O_{7}.

Beyond 14GPa of pressure, bilayered La_{3}Ni_{2}O_{7} was recently found to develop strong superconductivity above the liquid nitrogen boiling temperature. An immediate essential question is the pressure-induced qualitative change of electronic structure that enables the exciting high-temperature superconductivity. We investigate this timely question via a numerical multiscale derivation of effective many-body physics. At the atomic scale, we first clarify that the system has a strong charge transfer nature with itinerant carriers residing mainly in the in-plane oxygen between spin-1 Ni^{2+} ions. We then elucidate in electron-volt scale and sub-electron-volt scale the key physical effect of the applied pressure: it induces a cupratelike electronic structure via fractionalizing the Ni ionic spin from 1 to 1/2. This suggests a high-temperature superconductivity in La_{3}Ni_{2}O_{7} with microscopic mechanism and (d-wave) symmetry similar to that in the cuprates.

High‐Pressure‐Induced Lattice and Electronic Structural Transformations in Multilayer ZrS2

Compared with Group VIB transition metal dichalcogenides (TMDs), Group IVB TMDs, specifically ZrX2, have exhibited superior carrier mobility, rendering them highly promising for developing innovative electron devices. The application of high‐pressure has been identified as an effective approach for altering the physical properties of TMDs by manipulating their lattice and electronic structures. This subject has attracted considerable attention within the scientific community. In this investigation, in situ high‐pressure Raman scattering and UV‐visible absorption spectra analysis are conducted to examine the lattice and electronic structural changes in multilayer ZrS2. Raman spectroscopy analysis reveals two phase transitions occurring at 3.65 and 10.95 GPa. Concurrently, the optical absorption findings reveal a distinct transformation in both the optical energy gap and Urbach energy at 3.34 GPa, highlighting the accompanying lattice and electronic structural changes in ZrS2 under high‐pressure. Moreover, these lattice and electronic structural changes are found to be irreversible, indicating the potential utility of compressed ZrS2 in optoelectronic devices.

Influence of pH value of precursor on growth, structural, and optical properties of Cu2O thin films grown in Mist-CVD

The Cu2O thin films were prepared from copper (II) acetylacetonate (Cu(acac)2) by the mist chemical vapor deposition (mist-CVD) method, depending on the pH value of the prepared solution. It was confirmed that the well-oriented Cu2O thin films were grown at a dominant (111) peak according to X-ray diffraction (XRD) measurement using an alkaline precursor solution. The pH of the prepared solution drastically affected the surface morphology of the Cu2O thin films, and the lowest Root Means Square (RMS) was found for pH-10 of the precursor solution. The confocal Raman spectrum confirmed the formation of the cubic Cu2O crystal structures for each pH value of the precursor solution. The very transparent Cu2O thin films that were grown. The highest transmittance, 70%, was obtained at 1100 nm from the absorption spectrum for Sample B. The optical energy band gaps of Cu2O thin films were determined using Tauc's method and found to vary within a range of 2.53 to 2.49 eV, indicating a change in the material's electronic structure. The study demonstrated the crucial role of the pH level of the prepared solution in the growth of the Cu2O thin film. Specifically, it was found that a higher pH level resulted in a greater concentration of hydroxide ions (OH−), which was a crucial factor in the growth process. These findings can be significant in using p-type Cu2O thin films prepared based on mist-CVD for optoelectronic applications.