Electron Affinity Values Research Articles

Research of energy structure of crystalline compounds in Ag(Tl)-As(Р)-S(Se) systems

The paper presents the results of studying the peculiarities of formation of the valence band and the conduction band of crystalline compounds in Ag(Tl)-As(P)-S(Se) systems with sp3-type bond by using the photoelectron spectroscopy method. From the spectral distribution of photoemission by energy, the crystal photoelectron work function hν0 was determined. It was shown that the use of a limited basis (only ionization potentials of atoms and interatomic distances) for crystals with sp3-type bond within the framework of the LCAO model gives sufficiently accurate results of the position of the valence band top and the electron affinity value. Calculations show that the position of the valence band top defines the bonds of As-S(Se) and P-S(Se) atoms, while the hybridized orbitals of Ag and Tl atoms are formed in the conduction band.

Electronic structure, spectroscopic constants, and transition properties of NaC [formula omitted] diatomic species: An ab initio investigation

Diatomic species play a pivotal role in complex media, such as the interstellar and circumstellar media. Furthermore, there is a notable lack of information regarding NaC and its ions, NaC+ and NaC−, despite the pervasiveness of the carbon element (C) and the validated role of Na-bearing molecules as organic reagents or in catalytic processes. In this study, ab initio multi-reference calculations, including core valence and complete basis set schemes, were employed to accurately determine the potential energy curves (PECs), dipole moment functions (DMFs) and transition dipole moments (TDMs) of ten, three and ten low-lying electronic states energies, respectively, for NaC, NaC+ and NaC− diatomics species. The obtained results permitted the accurate determination of spectroscopic constants and vibrational transition properties, including vibrational level energies, Franck–Condon factors (FCFs), Einstein coefficients, absorption band oscillator strengths, vibrational transition energies and radiative lifetimes of allowed transitions. The predicted adiabatic ionisation energy value for NaC is 6.659 eV, while the vertical ionisation energy value is 6.676 eV. Similarly, the predicted adiabatic electron affinity value for NaC is 0.614 eV, while the vertical electron affinity value is 0.613 eV.

Sterically Tuned Ortho-Phenylene-Linked Donor-Acceptor Benzothiazole-Based Boron Difluoride Complexes as Thermally-Activated Delayed Fluorescence Emitters for Organic Light-Emitting Diodes.

Two donor-acceptor dyes with an ortho-phenylene-linked carbazole electron donor and a benzothiazole-fused boron heterocyclic acceptor were designed, synthesized, and spectroscopically investigated. Due to the steric effects of boron heterocyclic units, the dyes demonstrate different conformations in the crystalline state. The presence of numerous hydrogen-bonding intermolecular interactions and the very weak π-π stacking in the molecular packing results in intense solid-state emission with photoluminescence quantum yields of 40 and 18% for crystals and 50 and 42% for host-based light-emitting layers. The compounds show aggregation-induced emission and thermally activated delayed fluorescence (TADF). The received ionization potential and electron affinity values suggested good charge-injecting ability and bipolar charge-transporting properties of the developed dyes. Transport of holes and electrons was detected in layers of one dye by the time-of-flight measurements. The benzothiazole-based boron difluoride complexes showed high electron mobility of 1.5 × 10-4 and 0.7 × 10-4 cm2 V-1 s-1 at an electric field of 1.35 × 106 V cm-1. Therefore, these dyes were successfully applied as emitters in organic light-emitting diodes with external quantum efficiencies of 15 and 13%, respectively. Our study marks a critical advancement in the area of solid-state emissive boron difluoride dyes, which can be applied as TADF emitters into organic light-emitting diodes. The obtained results reveal that the orientation of the acceptor unit in the ortho-phenylene-linked donor-acceptor dyes makes a significant impact on the TADF activity.

Precision Measurement of the Electron Affinity of Chlorine via High-Resolution Photoelectron Spectroscopy.

Chlorine (Cl2) is a diatomic molecule used as an important industrial gas. However, the electron affinity (EA) of Cl2, a fundamental parameter for understanding chemical reactions, has no accurate experimental result available. The latest result of the EA value of Cl2 is 2.50(20) eV reported in 1983. In the present work, we report the precision measurement of the EA of Cl2 with the successive difference method via the high-resolution photoelectron spectroscopy of cryogenically cold chlorine anions Cl2-. The EA of Cl2 is determined to be 19432(9) cm-1 or 2.4093(11) eV.

Efficient and Accurate Estimation of Electronic Polarization Energies for Organic Semiconductors: An Embedding Charge Quantum Mechanics/Continuum Dielectric Model.

Electronic polarization plays a pivotal role in determining the molecular energy levels of organic semiconductors (OSCs) in the condensed phase. However, accurate estimation of the electronic polarization energy is a challenging task due to the intricate imbalance between the precision and efficiency. In this work, we have developed an embedding charge quantum mechanics/continuum dielectric (EC-QM/CD) model, which enables quantitative evaluation of the ionization potential (IP), electron affinity (EA), and polarization energy in both crystalline and amorphous solids for OSCs. The benchmark calculations on both p-type OSCs of oligoacenes and n-type OSCs of A-D-A small-molecule acceptors show that the values of IP, EA, and polarization energy obtained by EC-QM/CD are in good accordance with the experimental measurements or the results by high-precision methods, while the computational costs are substantially reduced. Given its balance between the accuracy and efficiency, the EC-QM/CD model exhibits considerable potential to broaden the applications in the field of OSCs, for instance, high-throughput screening by using solid-state energy levels or polarization energies as critical descriptors.

Numerical simulation to optimize power conversion efficiency of an FTO/GO/Cs2AgBiBr6/Cu2O solar cell.

Efficient conversion of solar power to electrical power through the development of smart, reliable, and environmentally friendly materials is a key focus for the next-generation renewable energy sector. The involvement of degradable and toxic elements present in hybrid perovskites presents serious concerns regarding the commercial viability of these materials for the solar cell industry. In this study, a solar cell with a stable, nondegradable, and lead-free halide-based double perovskite Cs2AgBiBr6 as the absorber layer, Cu2O as a hole transport layer, and GO as the electron transport layer has been simulated using SCAPS 1D. The thickness of the absorber, electron transport, and hole transport layers are tuned to optimize the performance of the designed solar cell. Notably, perovskite solar cells functioned most efficiently with an electron affinity value of 4.0 eV for Cu2O. In addition, the effect of variation of series resistance and temperature on generation and recombination rates, current density, and quantum efficiency has been elaborated in detail. The findings of this study provide valuable insight and encouragement toward the realization of a non-toxic, inorganic perovskite solar device and will be a significant step forward in addressing environmental concerns associated with perovskite solar cell technology.

Quantum chemical calculations of electron affinities of alkaline earth metal atoms (Ca, Sr, Ba, and Ra)

We performed high-level ab initio quantum chemical calculations, incorporating higher-order excitations, spin–orbit coupling (SOC), and the Gaunt interaction, to calculate the electron affinities (EAs) of alkaline earth (AE) metal atoms (Ca, Sr, Ba, and Ra), which are notably small. The coupled-cluster singles and doubles with perturbative triples [CCSD(T)] method is insufficient to accurately calculate the EAs of AE metal atoms. Higher-order excitations proved crucial, with the coupled-cluster singles, doubles, and triples with perturbative quadruples [CCSDT(2)Q] method effectively capturing dynamic electron correlation effects. The contributions of SOC (ΔESOs) to the EAs calculated using the multireference configuration interaction method with the Davidson correction, including SOC, positively enhance the EAs; however, these contributions are overestimated. The Dirac–Hartree–Fock (DHF)-CCSD(T) method addresses this overestimation and provides reasonable values for ΔESO (ΔESO−D). Employing additional sets of diffuse and core–valence correlation basis sets is critical for accurately calculating the EAs of AE metal atoms. The contributions of the Gaunt interaction (ΔEGaunt) to the EAs of AE metal atoms are negligible. Notably, the CCSDT(2)Q with the complete basis set limit + ΔESO−D + ΔEGaunt produced EA values for Ca, Sr, and Ba that closely aligned with experimental data and achieved accuracy exceeding the chemical accuracy. Based on our findings, the accurately proposed EA for Ra is 9.88 kJ/mol.

Origin of two-dimensional hole gas at the hydrogen-terminated diamond surfaces: Negative interface valence-induced upward band bending

The surface transfer doping model has been extensively adopted as a mechanism to account for the generation of hole accumulation layers below hydrogen-terminated diamond (H-diamond) surfaces. To achieve effective surface transfer doping, surface electron acceptor materials with high electron affinity (EA) are required to produce a high density of two-dimensional hole gas (2DHG) on the H-diamond subsurface. We have established ingenious theoretical models to demonstrate that even if these solid materials do not have a high EA value, they remain capable of absorbing electrons from the H-diamond surface by forming a negatively charged interface to act as a surface electron acceptor in the surface transfer doping model. Our calculations, particularly for the local density of states, provide compelling evidence that the effect of an interface with negative charges induces an upward band bending on the H-diamond side. Furthermore, the valence band maximum of the diamond atoms at the interface crosses the Fermi level, giving rise to strong surface transfer p-type doping. These results give a strong theoretical interpretation of the origin of 2DHG on H-diamond surfaces. The proposed guidelines contribute to further improvements in the performance of 2DHG H-diamond field effect transistors.

Exploring electron donor and acceptor effects: DFT analysis of ESIPT/GSIPT in 2-(oxazolinyl)-phenols for photophysical and luminophore enhancement.

Understanding excited-state intramolecular proton transfer (ESIPT) is essential for designing organic molecules to enhance photophysical and luminophore properties in the development of optoelectronic devices. In this context, an attempt has been made to understand the impact of substituents on the ESIPT process of 2-(oxazolinyl)-phenol. Electron donating (EDG: -NH2, -OCH3, and -CH3) and electron withdrawing (EWG: -Cl, -Br, -COOH, -CF3, -CN, and -NO2) substitutions have been computationally designed and screened through density functional theory (DFT) and time-dependent density-functional theory (TDDFT) calculations. Furthermore, the ground state intramolecular proton transfer and ESIPT mechanisms of these designed luminophores are explored using the transition state theory. The results reveal that molecules with EDG show higher absorption and emission peaks than molecules with EWG and also indicate that the mobility of charge carriers in 2-(oxazolinyl)-phenol derivatives is significantly influenced by substituents. We found that the EWGs decrease the reorganization energy and increase the vertical ionization potential and electron affinity values, as well as the highest occupied molecular orbital-lowest unoccupied molecular orbital gap, compared to the EDG substituted molecules. Significantly, the excited state (S1) of the keto emission (K) form shows notably larger values for the EDG substitutions. The intersystem crossing pathway efficiency weakens with reduced spin-orbit coupling matrix element in the enol form with electron-donating substituents and vice versa in the keto form during S1-T3 transitions. Our research links intramolecular proton transfers and triplet generation, making these substituted molecules appealing for optoelectronic devices. Introducing EDGs, such as -NH2, boosts the ESIPT reaction in 2-(oxazolinyl)-phenol. This study guides designing ESIPT emitters with unique photophysical properties.

Novel alkyne chromophore of the isophorone derivatives: synthesis, electrochemical evaluation, DFT, and processable bottom contact/top-gate OFET applications

Fused alkyne molecules are important in organic semiconductors due to their desirable properties. Here, we report the design and synthesis of a new series of A–π–D molecules (III–VII) that can serve as mild electron acceptors to generate wide-bandgap p-type small compounds for use in organic field-effect transistors. The incorporation of donor units into fused isophorone frameworks can be used to tune the frontier molecular orbital energies. The electrochemical, optical, and thermal properties of the compounds were characterized. Compound VI, which has a fused phenyl-substituted alkyne moiety, had the highest occupied molecular orbital energy level as determined by optical and electrochemical analysis. Density functional theory calculations revealed that compounds VI and III had lower hole reorganization energy (λh) than the corresponding isophorone extended conjugated-based compounds (I–II). Conversely, compounds I and II had lower electron reorganization energy (λe) than the corresponding fused alkyne compounds. This is in line with the observed adiabatic ionization potential and electron affinity values. Consequently, devices fabricated with compound VI exhibited high mobility and low threshold voltage.

Chemical library generation of polymer acceptors for organic solar cells with higher electron affinity

In this study, an intricate machine learning assisted framework is introduced for the designing of polymer acceptors. Machine learning (ML) models are trained to predict the electron affinity of polymers. Ten thousand new polymers are generated using the Breaking Retrosynthetically Interesting Chemical Substructures (BRICS) method and their electron affinity values are predicted using a pre-trained ML model. The selection of polymers is based on electron affinity, retaining those with higher electron affinity. The synthetic accessibility of the selected polymers is evaluated. Additionally, the structural similarity among the selected polymers is examined; results are indicating higher similarity between selected compounds. By efficiently identifying and optimizing new polymers, the approaches developed significantly enhance the likelihood of discovering superior materials for advanced applications.

Cyanocyclopentadiene-Annulated Polycyclic Aromatic Radical Anions: Predicted Negative Ion Photoelectron Spectra and Singlet-Triplet Energies of Cyanoindene and Cyanofluorene Radical Anions.

Isomer-specific negative ion photoelectron spectra (NIPES) of cyanoindene (C9H7CN) and cyanofluorene (C14H9N), acquired through the computation of Franck-Condon (FC) factors that utilize harmonic vibrational frequencies and normal mode vectors derived from density functional theory (DFT) at the B3LYP/aug-cc-pVQZ and 6-311++G(2d,2p) basis sets, are reported. The adiabatic electron affinity (EA) values of the ground singlet (S0) and the lowest lying triplet (T1) states are used to predict site-specific S0-T1 energies (ΔEST). The vibrational spectra of the S0 and T1 states are typified by ring distortion and ring C-C stretching vibrational progressions. Among all the S0 isomers in C9H7CN, the 2-cyanoindene (2-C9H7CN) is found to be the most stable at an EA of 0.716 eV, with the least stable isomer being the 1-C9H7CN at an EA of 0.208 eV. In C14H9N, the most stable S0 isomer, 2-cyanofluorene (2-C14H9N), has an EA of 0.781 eV. The least stable S0 isomer in C14H9N is the 9-C14H9N, with an EA of 0.364 eV. The FC calculations are designed to mimic simulations that would be performed to aid in the analysis of experimental spectra obtained in NIPE spectroscopic techniques. The vibrational spectra, adiabatic EAs, and ΔEST values reported in this study are intended to act as a guide for future gas-phase ion spectroscopic experiments and astronomical searches, especially with regard to the hitherto largely unexplored C14H9N isomers.

Impact of surface treatments on the electron affinity of nitrogen-doped ultrananocrystalline diamond

In recent years, various forms of nanocrystalline diamond (NCD) have emerged as an attractive group of diamond/graphite mixed-phase materials for a range of applications from electron emission sources to electrodes for neural interfacing. To tailor their properties for different uses, NCD surfaces can be terminated with various chemical functionalities, in particular hydrogen and oxygen, which shift the band edge positions and electron affinity values. While the band edge positions of chemically terminated single crystal diamond are well understood, the same is not true for nanocrystalline diamond, which has uncontrolled crystallographic surfaces with a variety of chemical states as well as graphitic grain boundary regions. In this work, the relative band edge positions of as-grown, hydrogen terminated, and oxygen terminated nitrogen-doped ultrananocrystalline diamond (N-UNCD) are determined using ultraviolet photoelectron spectroscopy (UPS), while the band bending is investigated using photoelectrochemical measurements. In contrast to the widely reported negative electrode affinity of hydrogen terminated single crystal diamond, our work demonstrates that hydrogen terminated N-UNCD exhibits a positive electron affinity owing to the increased surface and bulk defect densities. These findings elucidate the marked differences in electrochemical properties of hydrogen and oxygen terminated N-UNCD, such as the dramatic changes in electrochemical capacitance.

The impact of molecular orientations on the energy levels of A-D-A acceptors: implications for the charge separation driving force of organic solar cells.

The energetic landscape of charge carriers, namely the ionization potential (IP) and electron affinity (EA), can play a crucial role in the charge separation and migration processes for organic solar cells (OSCs). However, the impact of molecular orientations on the energy levels remains elusive, especially in acceptor-donor-acceptor (A-D-A) type nonfullerene acceptors (NFAs) with intrinsic anisotropy. Using the self-consistent quantum mechanics/embedded charge (sc-QM/EC) approach, we have investigated the energy level shifts from the edge-on or face-on surfaces to the bulk phase for three typical NFA crystals, IDIC-4F, INIC-4F, and Y6. The results point out that the surface-to-bulk changes in IP are limited within 0.2 eV for both the orientations due to the mutual counteraction between the electrostatic and induction effects. In sharp contrast, the EA values are substantially decreased from the bulk to the surfaces; especially, for the face-on orientation, the reduction reaches 0.5-0.8 eV. This indicates that the face-on orientation can provide a significant driving force for electrons moving from the surface or the interface to the bulk phase and thus improve the charge separation efficiency. Our work indicates that enhancing the face-on orientation is an effective method to increase the charge separation driving force for the OSCs based on A-D-A NFAs.

Photophysical and redox properties of new donor-acceptor-donor (DAD) compounds containing benzothiadiazole (A) and dimethyldihydroacridine (D) units: a combined experimental and theoretical study.

Four donor-acceptor-donor compounds consisting of 9,9-dimethyl-9,10-dihydroacridine donors differently linked to a benzothiadiazole acceptor were designed using DFT calculations and synthesized, namely 4,7-bis(4-(9,9-dimethyl-9,10-dihydroacridine)phenyl)benzo[c][1,2,5]thiadiazole (1), 4,7-bis(2,5-dimethyl-4-(9,9-dimethyl-9,10-dihydroacridine)phenyl)benzo[c][1,2,5]thiadiazole (2), 4,7-bis(3,5-di(9,9-dimethyl-9,10-dihydroacridine)phenyl)benzo[c][1,2,5]thiadiazole (3), and 4-(3,5-di(9,9-dimethyl-9,10-dihydroacridine)phenyl)-7-(thiophen-2-yl)benzo[c][1,2,5]thiadiazole (4). As predicted theoretically, all studied compounds were electrochemically active both in the reduction as well as in the oxidation modes. They underwent one electron quasi-reversible reduction. Oxidation of 1 and 2 involved a two electron process transforming them into dications and carrying out, in parallel, their dimerization. Oxidation of 3 and 4 resulted in their oligomerization (polymerization). The electrochemically determined ionisation potentials (IP) of 1-4 were similar, covering a narrow range of 5.28-5.33 eV and were consistent with DFT calculations. Larger differences were found for experimentally determined electron affinity (EA) values, being significantly lower for 2 (|EA| = 2.59 eV) as compared to 1, 3 and 4 whose |EA| values were higher by 0.15-0.25 eV, again consistent with DFT calculations. DFT calculations predict positive values of ΔE(S1-T1) for all compounds i.e. in the range of 0.18 eV to 0.43 eV for 1, 3 and 4 and a significantly lower value for 2 (0.06 eV), indicating a possible RISC process in this case. DFT calculations of ΔE(S1-T2) lead to negative and very small values for 2-4 implying a possible involvement of higher lying triplets in the generation of singlet excitons. The investigated derivatives exhibited fluorescence in the orange-red spectral range (550-770 nm) and were strongly dependent on the solvent polarity. The highest PLQY value of 37% was measured for 1 in toluene. The PLQY values significantly improved upon deoxygenation of the studied solutions. Solid state samples also exhibited higher PLQY values as compared to those determined for DCM solutions. These findings were rationalized by partial suppression of the vibrationally induced emission quenching in the solid state due to the intermolecular interaction confinement.

Oriented External Electric Field Modulated Superhalogen Characteristic and Photoelectric Properties of Al4N2 Cluster: A Density Functional Theory Study

AbstractDesigning superatoms with special structural and photoelectric properties is vital for the applications in multiple fields including condensed matter physics, nanomaterials science etc. In this study, the effects of an oriented external electric field (OEEF) on the geometry, electronic properties, photoelectron spectrum (PES), and nonlinear optical (NLO) response of the main group metal‐doped cluster Al4N2 were investigated using density functional theory (DFT) calculations. The results demonstrate that the OEEF has the capability to increase the value of the electron affinity (EA) of Al4N2 continuously and dramatically, transforming it into a member of superhalogens while maintaining its geometrical stability. Such an enhancement of the EA value of Al4N2 is attributed to the downward shift of the electronic spectrum under the effect of the OEEF. Strikingly, the relationship between the EA value of Al4N2 and the OEEF strength can be fitted by a perfect polynomial formula, which indicates that the OEEF can realize the accurate and continuous regulation of the electronic properties of Al4N2. In addition, the simulated PES of the Al4N2− cluster was observed to be blue shifted following the enhancement of the OEEF intensities, and the NLO response of the cluster can also be remarkably altered by the OEEF.

A Computational Study on the Impact of Anchoring Groups on the Optical and Electronic Properties of Triphenylamine-Based Dyes for Dye-Sensitized Solar Cell Applications

Anchoring groups are crucial for enhancing the performance of dye-sensitized solar cells (DSSCs). For instance, cyanoacrylic acid serves as the primary anchoring group in DSSC due to its crucial elements required for effective electron transport. However, it suffers from degradation. To address this limitation, this study proposes alternative cyano-based anchoring groups for sensitizers. Density functional theory (DFT) and time-dependent DFT were used to investigate the optical and electronic properties of the dyes. The studied dyes (excluding the dye containing OH group) displayed three absorption bands within the visible and NIR regions. Low-energy peaks ranged from 498 to 576 nm, corresponding to excitation from ground state to first excited state. Moderate intensity bands appeared at 376 to 418 nm, with the highest energy bands falling within 351 to 384 nm. Ground state oxidation potential values for the dyes were lower than the redox potential of the iodide/triiodide pair. Similarly, excited state oxidation potential values were higher than or equal to the conduction band of TiO2, except for NO2 and CHO containing dyes. Ionization potential values ranged from 6.24 eV to 6.40 eV, while electron affinity values were within 1.21 eV to 2.74 eV. Chemical potential values ranged from 3.75 to 4.57 eV, and chemical hardness of the dyes fell between 1.83 to 2.54 eV. The proposed cyano-based anchoring groups show promising potential for enhancing DSSC performance.

N-type doping of diamond surface by potassium

For diamond with exceptional physical and chemical properties, it is a challenging task to develop an effective n-type dopant with satisfactory electronic properties. In this work, using the first-principles calculation, we report the n-type doping of diamond surface (areal electron density of 2.508 × 1013–4.090 × 1013 cm−2 and carrier mobility of 189–1186 cm2 V−1 s−1 at 298 K) by surface transfer doping using potassium (K). Electrons are transferred from the K atoms to the diamond surface, then electrons accumulation appears on the diamond surface. In addition, the areal electron density and electron affinity values increase with increasing K concentration. This work provides a new strategy for producing n-type diamond-based devices.

Diltiazem and Verapamil: Combined experimental and computational approaches to structural and spectroscopic characterization

Diltiazem and Verapamil are two important drug molecules in a separate group of Calcium Channel Blockers. The purpose of this work is to determine and compare the structural and spectroscopic properties of these two molecules using a number of experimental techniques and quantum chemical calculations. Compounds were characterized spectroscopically using FT-IR, Raman, NMR (1H, 13C, and DEPT), and UV–vis methods. Furthermore, the Density Functional Theory (DFT) method, Becke's three-parameter hybrid functional (B3LYP), and the 6–311++G(d,p) basis set were used to determine the ground state geometric structures of molecules, and the spectroscopic properties of the obtained optimum structures were investigated computationally. The optimization studies performed under vacuum circumstances and for the isolated molecules were found to be very close to the experimental results. In fact, r.m.s. values were discovered for Diltiazem and Verapamil with bond lengths of 0.013 and 0.024, and bond angles of 1° and 2°, respectively. The vibration characteristics of the compounds were discovered using the collected FT-IR and Raman spectra, and significant vibrational modes were assigned. After scaling, it was revealed that the quantum chemical data was congruent with the experimental ones, and that the characteristic vibrational modes were appropriately predicted. DFT calculations effectively determine molecules' structures due to internal consistency, despite being slightly distant from experimental data. Theoretical values for carbon and hydrogen atoms are better in agreement with observed values when scaling with 0.92 and 0.90. From the UV–vis spectra, Diltiazem HCl absorbance peaks were found at 207 and 237 nm, whereas Verapamil HCl absorbance peaks were identified at 203, 229, and 278 nm. When the theoretical calculations and experimental findings were compared, the anticipated absorption peaks were found to have shifted nearer the visible area. Furthermore, Hirshfeld surfaces and Molecular Electrostatic Potential surfaces were obtained and analyzed in order to better understand the electronic characteristics. The TDOS and PDOS (total and partial density of state) spectra were also studied. Finally, using the HOMO and LUMO energy values, the critical chemical parameters were evaluated, and it was discovered that both molecules had positive electron affinity and electronegativity values, indicating that they will accept electrons when the electron-nucleus attraction exceeds the electron-electron repulsion.

Factors Controlling the High Oxidative Activities of Layered Manganese Oxides

The two-dimensional layered birnessite mineral is a powerful natural oxidant and an important model compound in the development of bioinspired electrocatalysts for the water oxidation reaction (OER). The aim of this work was to study the factors controlling their unusually high oxidative activities of natural and synthetic samples for both spontaneous and potential-induced oxidation reactions. The results of the study1 of various cation-exchanged birnessites for spontaneous Cr(III) to Cr(VI) oxidation reactions show that the oxidative activity of birnessite, which decreases in order Mg > Cs = K > Na > Ca > Li > H, is due to its unusually high electron affinity of ∼5.9 eV, which is the highest among all known functional oxides and sulphides in aqueous solution. Both the band gap (Cs > Mg > K > Na > Ca > Li > H) and the electron affinity (Na > Cs > K > Mg > Ca > Li > H) are seen to be strongly affected by the nature of the interlayer cations and their coordinating water molecules. Analysis shows that the band gap scales with the interlayer spacing, while the electron affinity scales with the relative Mn(III)/Mn(II) concentration.In another study2, the performance of birnessite as an electrocatalytic water oxidation catalyst and the mechanism of key Mn(III) intermediate formation were evaluated through the study of the effects of various electrolyte anions and cations on the catalytic efficiency. In situ spectroelectrochemical measurements show that the activity is controlled by a dynamic dissolution-oxidation process, wherein Mn(III) is formed through the oxidation of labile uncomplexed Mn(II) that shuttles between the crystal lattice and the electrolyte. The role of electrolyte anions is to control the extent of deprotonation of complexed Mn(II) in the lattice while the electrolyte cations control the interlayer spacing. Both in turn govern the shuttling efficiency of uncomplexed Mn(II) and its subsequent electrooxidation to Mn(III). The high electron affinity values put the band edges of birnessite-type structures well below the redox potential of most thermodynamically stable cations and water, enabling their spontaneous oxidation. The high electron affinity is another example of the unusual features of Mn compounds, which Nature uses for its many biogeochemical functions. C. Wang; N. Smieszek; V. Chakrapani, Unusually High Electron Affinity Enables the High Oxidising Power of Layered Birnessite Chem. Mater. 2021, 33 (19), 7805-7817.I. Roy; C. Wang; N. Smieszek; X. Li; L. Tsapatsaris; V. Chakrapani, Formation of the Metastable MnIII Water Oxidation Intermediate in Birnessite is Controlled by a Dissolution-Deposition Process Involving Labile MnII. ChemSusChem 2022, 15 (8), e202200062. Figure 1