Electronic Structure Of Complexes Research Articles

Pseudocapacitance Facilitates the Electrocatalytic Reduction of Carbon Dioxide

AbstractElectroreduction of CO2 to value‐added products is a promising strategy for CO2 reuse, where copper has a unique ability to produce oxygenates and C2+ products. Unfortunately, the electronic factors making copper so unique are unknown, which limits the ability to design improved catalysts. By combining in situ surface‐sensitive X‐ray resonant photoelectron spectroscopy with density functional theory calculations, the complex electronic structure of copper is uncovered during the electrocatalytic reduction of CO2. It is found that the pseudocapacitive charging of copper, produced by the incorporation of protons and electrons into the subsurface, facilitates the activation of CO2, while simultaneously increasing the barrier for H‐H coupling. The net result is that cathodic pseudocapacitive charge suppresses the hydrogen evolution reaction and promotes the production of hydrocarbons and oxygenated products on copper. These results represent a new paradigm in the understanding of CO2 reduction, highlighting the key role of pseudocapacitive charge in the reaction.

Local Energy Decomposition Analysis of London Dispersion Effects: From Simple Model Dimers to Complex Biomolecular Assemblies.

ConspectusLondon dispersion (LD) forces are ubiquitous in chemistry, playing a pivotal role in a wide range of chemical processes. For example, they influence the structure of molecular crystals, the selectivity of organocatalytic transformations, and the formation of biomolecular assemblies. Harnessing these forces for chemical applications requires consistent quantification of the LD energy across a broad and diverse spectrum of chemical scenarios. Despite the great progress made in recent years in the development of experimental strategies for LD quantification, quantum chemical methods remain one of the most useful tools in the hand of chemists for the study of these weak interactions. Unfortunately, the accurate quantification of LD effects in complex systems poses many challenges for electronic structure theories. One of the problems stems from the fact that LD forces originate from long-range electronic dynamic correlation, and hence, their rigorous description requires the use of complex, highly correlated wave function-based methods. These methods typically feature a steep scaling with the system size, limiting their applicability to small model systems. Another core challenge lies in disentangling short-range from long-range dynamic correlation, which from a rigorous quantum mechanical perspective is not possible.In this Account, we describe our research endeavors in the development of broadly applicable computational methods for LD quantification in molecular chemistry as well as challenging applications of these schemes in various domains of chemical research. Our strategy lies in the use of local correlation theories to reduce the computational cost associated with complex electronic structure methods while providing at the same time a simple means of decomposition of dynamic correlation into its long-range and short-range components. In particular, the local energy decomposition (LED) scheme at the domain-based local pair natural orbital coupled cluster (DLPNO-CCSD(T)) level has emerged as a powerful tool in our research, offering a clear-cut quantitative definition of the LD energy that remains valid across a plethora of different chemical scenarios. Typical applications of this scheme are examined, encompassing protein-ligand interactions and reactivity studies involving many fragments and complex electronic structures. In addition, our research also involves the development of novel cost-effective methodologies, which exploit the LED definition of the LD energy, for LD energy quantification that are, in principle, applicable to systems with thousands of atoms. The Hartree-Fock plus London Dispersion (HFLD) scheme, correcting the HF interaction energy using an approximate CCSD(T)-based LD energy, is a useful, parameter-free electronic structure method for the study of LD effects in systems with hundreds of molecular fragments. However, the usefulness of the LED scheme reaches beyond providing an interpretation of the calculated DLPNO-CCSD(T) or DLPNO-MP2 interaction energies. For example, the dispersion energies obtained from the LED can be fruitfully used in order to parametrize semiempirical dispersion models. We will demonstrate this in the context of an emerging semiempirical method, namely, the Natural Orbital Tied Constructed Hamiltonian (NOTCH) method. NOTCH incorporates LED-derived LD energies and shows promising accuracy at a minimum amount of empiricism. Thus, it holds substantial promise for large and complex systems.

Active-learning for global optimization of Ni-Ceria nanoparticles: The case of Ce4-xNixO8- x (x = 1, 2, 3).

Ni-CeO2 nanoparticles (NPs) are promising nanocatalysts for water splitting and water gas shift reactions due to the ability of ceria to temporarily donate oxygen to the catalytic reaction and accept oxygen after the reaction is completed. Therefore, elucidating how different properties of the Ni-Ceria NPs relate to the activity and selectivity of the catalytic reaction, is of crucial importance for the development of novel catalysts. In this work the active learning (AL) method based on machine learning regression and its uncertainty is used for the global optimization of Ce(4-x)NixO(8-x) (x = 1, 2, 3) nanoparticles, employing density functional theory calculations. Additionally, further investigation of the NPs by mass-scaled parallel-tempering Born-Oppenheimer molecular dynamics resulted in the same putative global minimum structures found by AL, demonstrating the robustness of our AL search to learn from small datasets and assist in the global optimization of complex electronic structure systems.

Thermal properties of Cu2S binary copper sulfides

Copper chalcogenides have a complex electronic structure due to the interaction of hybridized s- and p-states of chalcogen forming a valence band with 3d states of copper, which greatly complicates the interpretation of temperature dependences of kinetic parameters having a nonmonotonic character. Cu2S copper sulfide is an effective thermoelectric material, so it is interesting to study its kinetic parameters of solid solutions that it forms with alkali metals. The nonstoichiometry of chalcogenides can be easily controlled electrochemically, therefore, the task of selecting the optimal composition according to the cationic sublattice is quite feasible. The paper presents experimental studies of the properties of Cu2S binary copper sulfide. Copper chalcogenides have a complex electronic structure due to the interaction of hybridized s- and p-states of chalcogen forming a valence band with 3d states of copper, which greatly complicates the interpretation of temperature dependences of kinetic parameters having a nonmonotonic character. For the Cu2S sample, rather low values of the electron thermal EMF coefficient of the sample from 0.05 mV/K to 0.25 mV/K were found, which are more typical for metals than for semiconductors. The thermal conductivity of the Cu2S sample is quite low, it rises to 0.3 W/m*K at a phase transition of about 380 K and does not fall below 0.2 W/m*K. Thus, the nonstoichiometry of chalcogenides can be easily controlled electrochemically, therefore, the task of selecting the optimal composition according to the cationic sublattice is quite feasible. In addition, to improve the thermoelectric properties of Cu2S, it can be achieved by alloying alkali metals into a binary copper sulfide matrix.

High-entropy strategy for high-temperature broadband infrared radiation and low thermal conductivity

Developing high-performance infrared radiation ceramic materials with desired broadband emissivity while reducing thermal conductivity to prevent heat transfer is highly desirable for emerging industrial and aerospace applications. Nevertheless, it remains a grand challenge to simultaneously meet these requirements in existing infrared radiation ceramic materials. Herein, a high-entropy strategy is employed to enhance the high-temperature infrared radiation property with a high emissivity above 0.9 at room temperature and 0.68 at 1200 °C across the entire range of wavelength (1–14 μm), and integrate a low thermal conductivity (<0.88 W m−1 K−1 at 1000 °C) and remarkable mechanical properties. High-entropy rare earth (RE) disilicates ((Y0.4Yb0.4Tm0.1Lu0.05Ho0.05)2Si2O7) ceramic coating with high lattice entropy has a more complex electronic structure, inducing lattice distortion and extra multi-mode vibrations, which boosts the emissivity in mid-infrared range (3–14 μm). Meanwhile, the high-entropy strategy prompts the formation of impurity energy levels as gap states, achieving optical absorption at low photon energies, and thus enhancing the emissivity in near-infrared range (1–3 μm). Simultaneously, (Y0.4Yb0.4Tm0.1Lu0.05Ho0.05)2Si2O7) ceramic coating owns diffusion-mediated thermal transport properties with strong phonon scattering, assisted further by the lamellar porous structure, thereby enabling a low thermal conductivity. The excellent mechanical properties ensure the reliability of the coating in extreme environments. All these merits render the high-entropy ceramic coating competitive for the development of high-temperature broadband high-emissivity thermal radiation materials.

Developing a Multiband Electronic Band Structure Model and Predictive Maps for Bismuth-Rich Mg3(Sb1-xBix)2 Thermoelectric Materials.

In recent years, bismuth-rich Mg3(Sb1-xBix)2 (x = 0.5-0.8) compositions have generated significant interest due to their excellent thermoelectric (TE) performance near room temperature, making them potential applicants for recovery of low-grade waste heat. The superior performance in these materials is due to its complex electronic band structure (EBS) with presence of multiple near degenerate bands close to the conduction band edge. The position and curvature of these bands strongly depend on the alloy composition, doping amount as well as temperature. Thus, identifying optimal material compositions to get the best TE performance depends on an understanding of the temperature dynamics of EBS and forms the objective of this work. Mg3Sb0.6Bi1.4 (x = 0.7) is chosen for this study due to its reported high near room temperature performance, and compositions with varying doping concentrations (Te used as dopant) have been synthesized. EBS parameters like effective mass and deformation potential of bands, interband separation and band gap values have been estimated using a recently developed refinement approach. Refinement results indicate that the interband separation between conduction bands to be a function of both temperature and doping concentration. Further, thermal conductivity (κ) was estimated for all of the compositions. Utilizing the EBS and κ information, predictive 3D maps indicating the variation in zT (TE figure of merit) with doping concentration and temperature have been generated. The 3D maps reveal an interesting surface topography with a broad peak zT region. This observation explains why these materials have high TE performance and are less sensitive to doping inhomogeneities. Our results provide detailed EBS information and fundamental insights on the TE properties of Mg3Sb0.6Bi1.4. Further, the proposed technique can be utilized to probe other Mg3(Sb1-xBix)2 compositions and TE materials.

Ultrafast excited-state dynamics of Luteins in the major light-harvesting complex LHCII

Carotenoid pigments are known to present a functional versatility when bound to light-harvesting complexes. This versatility originates from a strong correlation between a complex electronic structure and a flexible geometry that is easily tunable by the surrounding protein environment. Here, we investigated how the different L1 and L2 sites of the major trimeric light-harvesting complex (LHCII) of green plants tune the electronic structure of the two embedded luteins, and how this reflects on their ultrafast dynamics upon excitation. By combining molecular dynamics and quantum mechanics/molecular mechanics calculations, we found that the two luteins feature a different conformation around the second dihedral angle in the lumenal side. The s-cis preference of the lutein in site L2 allows for a more planar geometry of the π\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\pi$$\\end{document}-conjugated backbone, which results in an increased degree of delocalization and a reduced excitation energy, explaining the experimentally observed red shift. Despite these remarkable differences, according to surface hopping simulations the two luteins present analogous ultrafast dynamics upon excitation: the bright S2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$S_2$$\\end{document} state quickly decays (in ∼\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\sim$$\\end{document} 50 fs) to the dark intermediate Sx\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$S_x$$\\end{document}, eventually ending up in the S1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$S_1$$\\end{document} state. Furthermore, by employing two different theoretical approaches (i.e., Förster theory and an excitonic version of surface hopping), we investigated the experimentally debated energy transfer between the two luteins. With both approaches, no evident energy transfer was observed in the ultrafast timescale.Graphical abstract

Machine Learning Interatomic Potentials for Reactive Hydrogen Dynamics at Metal Surfaces Based on Iterative Refinement of Reaction Probabilities.

The reactive chemistry of molecular hydrogen at surfaces, notably dissociative sticking and hydrogen evolution, plays a crucial role in energy storage and fuel cells. Theoretical studies can help to decipher underlying mechanisms and reaction design, but studying dynamics at surfaces is computationally challenging due to the complex electronic structure at interfaces and the high sensitivity of dynamics to reaction barriers. In addition, ab initio molecular dynamics, based on density functional theory, is too computationally demanding to accurately predict reactive sticking or desorption probabilities, as it requires averaging over tens of thousands of initial conditions. High-dimensional machine learning-based interatomic potentials are starting to be more commonly used in gas-surface dynamics, yet robust approaches to generate reliable training data and assess how model uncertainty affects the prediction of dynamic observables are not well established. Here, we employ ensemble learning to adaptively generate training data while assessing model performance with full uncertainty quantification (UQ) for reaction probabilities of hydrogen scattering on different copper facets. We use this approach to investigate the performance of two message-passing neural networks, SchNet and PaiNN. Ensemble-based UQ and iterative refinement allow us to expose the shortcomings of the invariant pairwise-distance-based feature representation in the SchNet model for gas-surface dynamics.

A new mixed-ligand mononuclear Co(II) complex derived from 4,4,4-trifluoro-1-phenylbutane-1,3-dione and 1,10-phenanthroline: Synthesis, structural elucidation and quantum-computational studies

In this study, a novel mixed-ligand mononuclear Co(II) complex, denoted as {[Co(TFPBD)2(PHE)]DMF}, was synthesized and characterized using single crystal X-ray diffraction analysis. The central cobalt atom coordinated with two 4,4,4-trifluoro-1-phenylbutane-1,3-dione ligands (TFPBD1 and TFPBD2) and a 1,10-phenanthrene (PHE) ligand, adopting a slightly distorted octahedral geometry. Notably, the non-planar characteristics of the ligands led to the manifestation of non-covalent interactions within the molecular structure, further enhanced by the involvement of the lattice DMF solvent. The crystal lattice arrangement in the {[Co(TFPBD)2(PHE)]DMF} complex was a result of diverse non-covalent interactions, including hydrogen bonds, C-F…π, and Π…π stacking interactions, influenced the crystal's stability. Additionally, the study delved into the unique lattice arrangement consisted of pairwise R12(5) ring motifs along with one-dimensional molecular arrays formed along the crystallographic axes. Furthermore, intermolecular C-F…π Cg…Cg interactions resulting in two-dimensional linear molecular arrays along the a- and b-axes. Quantum computational studies using density functional theory (DFT) were employed to examine the complex's electronic structure and stability and reactivity, highlighting electron-rich and electron-deficient regions. Hirshfeld surface analysis (HSA) and Non-covalent interaction analysis confirmed the significance of intermolecular interactions where 2D fingerprint plots emphasized the prominence of CH…F interactions within the crystal structure. These findings contribute significantly to our understanding of mixed-ligand metal complexes and their potential applications in various scientific domains.

Altering the Localization of an Unpaired Spin in a Formal Ni(V) Species.

The participation of both ligand and the metal center in the redox events has been recognized as one of the ways to attain the formal high valent complexes for the late 3d metals, such as Ni and Cu. Such an approach has been employed successfully to stabilize a Ni(III) bisphenoxyl diradical species in which there exist an equilibrium between the ligand and the Ni localized resultant spin. The present work, however, broadens the scope of the previously reported three oxidized equivalent species by conveying the approaches that tend to affect the reported equilibrium in CH3 CN at 233 K. Various spectroscopic characterization revealed that employing exogenous N-donor ligands like 1-methyl imidazole and pyridine favors the formation of the Ni centered localized spin though axial binding. In contrast, due to its steric hinderance, quinoline favors an exclusive ligand localized radical species. DFT studies shed light on the novel intermediates' complex electronic structure. Further, the three oxidized equivalent species with the Ni centered spin was examined for its hydrogen atom abstraction ability stressing their key role in alike reactions.

How to read optical properties of matter via the Kubo-Greenwood approach.

Substances with a complex electronic structure exhibit non-Drude optical properties that are challenging to interpret experimentally and theoretically. In our recent paper [Phys. Rev. E 105, 035307 (2022)2470-004510.1103/PhysRevE.105.035307], we offered a computational method based on the continuous Kubo-Greenwood formula, which expresses dynamic conductivity as an integral over the electron spectrum. In this Letter, we propose a methodology to analyze the complex conductivity using liquid Zr as an example to explain its nontrivial behavior. To achieve this, we apply the continuous Kubo-Greenwood formula and extend it to include the imaginary part of the complex conductivity into the analysis. Our method is suitable for a wide range of substances, providing an opportunity to explain optical properties from ab initio calculations of any difficulty.

Fully First-Principles Surface Spectroscopy with Machine Learning.

Our current understanding of the structure and dynamics of aqueous interfaces at the molecular level has grown substantially due to the continuous development of surface-specific spectroscopies, such as vibrational sum-frequency generation (VSFG). As in other vibrational spectroscopies, we must turn to atomistic simulations to extract all of the information encoded in the VSFG spectra. The high computational cost associated with existing methods means that they have limitations in representing systems with complex electronic structure or in achieving statistical convergence. In this work, we combine high-dimensional neural network interatomic potentials and symmetry-adapted Gaussian process regression to overcome these constraints. We show that it is possible to model VSFG signals with fully ab initio accuracy using machine learning and illustrate the versatility of our approach on the water/air interface. Our strategy allows us to identify the main sources of theoretical inaccuracy and establish a clear pathway toward the modeling of surface-sensitive spectroscopy of complex interfaces.

Europium(III) and gallic acid ligand coordination compounds: synthesis, characterization, photophysical processes, and optimization of luminescent properties

We obtained EuIII, GdIII, and GdIII doped with EuIII (1 at.% and 5 at.%) complexes with the ligand derived from 3,4,5-trihydroxybenzoic acid (H4Gal). Synthetic routes are proposed from acetate and chloride solutions of the trivalent lanthanides. We demonstrated the decomposition of the ligands 3,4,5-trihydroxybenzoate (H3Gal ≡ L–) and 3-hydroxo-4,5-dihydroxybenzoate (H2Gal2– ≡ L’2–) in an acetic solution medium. [LnLL’(H2O)2] complexes are obtained in a metal chloride solution medium. We studied the complexes in the solid state. We described the photophysical processes in the complexes, and they resulted in an energy diagram of the EuIII compounds in which the position of the states related to the LMCT transition are intermediate to the ligand's singlet (S1) and triplet (T1) states. We obtained the position of the triplet state (T1) from the luminescence of the GdIII complex. We performed the calculations of the EuIII complex's electronic structure using the Lumpac software to confirm the propositions obtained through experiments. The proposition is that the excitation in the LMCT state rapidly populates the T1 state, and the L–L’2–→EuIII back energy transfer may occur. One of the possible disadvantages of the complexes is the enormous non-radioactive deactivation due to the oscillators (OH) and (CH). The EuIII characteristic luminescence is of little intensity. We obtained GdIII compounds doped with EuIII at 1.0 and 5.0 at.% to optimize luminescent properties. We obtained the emission and excitation spectra of the complexes at 77 and 17 K, showing ligands' phosphorescence superimposed on the characteristic emissions 5D0 →7FJ (J = 0–4) of the EuIII ion.

High-entropy halide perovskite single crystals stabilized by mild chemistry.

Although high-entropy materials are excellent candidates for a range of functional materials, their formation traditionally requires high-temperature synthetic procedures of over 1,000 °C and complex processing techniques such as hot rolling1-5. One route to address the extreme synthetic requirements for high-entropy materials should involve the design of crystal structures with ionic bonding networks and low cohesive energies. Here we develop room-temperature-solution (20 °C) and low-temperature-solution (80 °C) synthesis procedures for a new class of metal halide perovskite high-entropy semiconductor (HES) single crystals. Due to the soft, ionic lattice nature of metal halide perovskites, these HES single crystals are designed on the cubic Cs2MCl6 (M=Zr4+, Sn4+, Te4+, Hf4+, Re4+, Os4+, Ir4+ or Pt4+) vacancy-ordered double-perovskite structure from the self-assembly of stabilized complexes in multi-element inks, namely free Cs+ cations and five or six different isolated [MCl6]2- anionic octahedral molecules well-mixed in strong hydrochloric acid. The resulting single-phase single crystals span two HES families of five and six elements occupying the M-site as a random alloy in near-equimolar ratios, with the overall Cs2MCl6 crystal structure and stoichiometry maintained. The incorporation of various [MCl6]2- octahedral molecular orbitals disordered across high-entropy five- and six-element Cs2MCl6 single crystals produces complex vibrational and electronic structures with energy transfer interactions between the confined exciton states of the five or six different isolated octahedral molecules.

Accurate Simulations of Scanning Tunneling Microscope: Both Tip and Substrate States Matter.

Scanning tunneling microscope (STM) provides an atomic-scale characterization tool. To this end, high-resolution measurements and accurate simulations must closely cooperate. Emerging experimental techniques, e.g., substrate spacers and tip modifications, suppress metallic couplings and improve the resolution. On the other hand, development of STM simulation methods was inactive in the past decade. Conventional simulations focus on the electronic structure of the substrate, often overlooking detailed descriptions of the tip states. Meanwhile, the overwhelming usage of periodic boundary conditions ensures effective simulations of only neutral systems. In this Perspective, we highlight the recent progress that takes the effects of both tip and substrate into account under either Tersoff-Hamann or Bardeen's approximation, which provides an accurate analysis of measured high-resolution STM results, uncovers underlying concepts, and rationally designs experimental protocols for important chemical systems. We hope this Perspective will stimulate broad interest in advanced STM simulations, highlighting the way forward for STM investigations that involve complex geometrical and electronic structures.

Two-dimensional Kβ-Kα fluorescence spectrum by nonlinear resonant inelastic X-ray scattering

High sensitivity of the Kβ fluorescence spectrum to electronic state is widely used to investigate spin and oxidation state of first-row transition-metal compounds. However, the complex electronic structure results in overlapping spectral features, and the interpretation may be hampered by ambiguity in resolving the spectrum into components representing different electronic states. Here, we tackle this difficulty with a nonlinear resonant inelastic X-ray scattering (RIXS) scheme, where we leverage sequential two-photon absorption to realize an inverse process of the Kβ emission, and measure the successive Kα emission. The nonlinear RIXS reveals two-dimensional (2D) Kβ-Kα fluorescence spectrum of copper metal, leading to better understanding of the spectral feature. We isolate 3d-related satellite peaks in the 2D spectrum, and find good agreement with our multiplet ligand field calculation. Our work not only advances the fluorescence spectroscopy, but opens the door to extend RIXS into the nonlinear regime.

Valence and Core Photoelectron Spectra of Aqueous I3- from Multi-Reference Quantum Chemistry.

The I3- molecule is known to undergo substantial structural reorganization upon solvation by a protic solvent, e.g., water. However, the details of this process are still controversially discussed in the literature. In the present study, we combined experimental and theoretical efforts to disentangle this controversy. The valence (5p), N4,5 (4d), and M4,5 (3d) edge photoelectron spectra were measured in an aqueous solution and computed using high-level multi-reference methods. Our previous publication mainly focused on obtaining reliable experimental evidence, whereas in the present article, we focused primarily on theoretical aspects. The complex electronic structure of I3- requires the inclusion of both static and dynamic correlation, e.g., via the multi-configurational perturbation theory treatment. However, the resulting photoelectron spectra appear to be very sensitive to problems with variational stability and intruder states. We attempted to obtain artifact-free spectra, allowing for a more reliable interpretation of experiments. Finally, we concluded that the 3d Photoelectron Spectrum (PES) is particularly informative, evidencing an almost linear structure with a smaller degree of bond asymmetry than previously reported.

Bond dissociation energies for Fe2+, Fe2O+, and Fe2O2+ clusters determined through threshold photodissociation in a cryogenic ion trap.

Understanding and controlling the chemical behavior of iron and iron oxide clusters requires accurate thermochemical data, which, because of the complex electronic structure of transition metal clusters, can be difficult to calculate reliably. Here, dissociation energies for Fe2+, Fe2O+, and Fe2O2+ are measured using resonance enhanced photodissociation of clusters contained in a cryogenically cooled ion trap. The photodissociation action spectrum of each species exhibits an abrupt onset for the production of Fe+ photofragments from which bond dissociation energies are deduced for Fe2+ (2.529 ± 0.006eV), Fe2O+ (3.503 ± 0.006eV), and Fe2O2+ (4.104 ± 0.006eV). Using previously measured ionization potentials and electron affinities for Fe and Fe2, bond dissociation energies are determined for Fe2 (0.93 ± 0.01eV) and Fe2- (1.68 ± 0.01eV). Measured dissociation energies are used to derive heats of formation ΔfH0(Fe2+) = 1344 ± 2 kJ/mol, ΔfH0(Fe2) = 737 ± 2 kJ/mol, ΔfH0(Fe2-) = 649 ± 2 kJ/mol, ΔfH0(Fe2O+) = 1094 ± 2 kJ/mol, and ΔfH0(Fe2O2+) = 853 ± 21 kJ/mol. The Fe2O2+ ions studied here are determined to have a ring structure based on drift tube ion mobility measurements prior to their confinement in the cryogenic ion trap. The photodissociation measurements significantly improve the accuracy of basic thermochemical data for these small, fundamental iron and iron oxide clusters.

Cluster spin glass in off-stoichiometric Ni2.01Mn1.58Sn0.41 alloy

The Ni2.01Mn1.58Sn0.41 alloy is a member of the Heusler material family which undergoes diffusionless structural transition from cubic austenite to orthorhombic martensite during its cooling. The transition was observed at temperature 398 K from paramagnetic austenite to martensite with complex magnetic structure. The measurement of AC magnetic susceptibility of the alloy confirmed spin-glass state at temperatures below 155 K and from the frequency dependence of the cups in AC susceptibility, a presence of clusters (11 nm3 in size) with strong interaction is deduced. The alloy shows anomalous Hall effect (AHE) of the order of 0.051 μΩ cm at 2 K in the spin-glass state of the alloy and its sign changes at around 140 K. The ordinary Hall coefficient of the metallic alloy is strikingly positive in the whole studied temperature region, and it points to complex magnetic and electronic structure of the alloy. The electrical resistance of the sample shows a flat maximum of 220 μΩ cm at spin-glass transition temperature. The magnetoresistance is of the order of 1% and is negative in the whole temperature region which points to a standard scattering of charge carriers on magnetic fluctuations. Quantum-mechanical calculations of supercells with compositions Ni32Mn25Sn7, Ni32Mn26Sn6 and Ni32Mn24Sn8 simulated different arrangement of Mn and Sn atoms. Ni32Mn25Sn7 composition is thermodynamically the most stable, although its magnetic moment is 1.67 μB/f.u., twice higher than the measured value. The combination of the latter two states, with additional Mn–Sn swaps, provides the magnetic moments matching the experimental value at a very small energy cost. Theoretical results then indicate that a scenario of local chemical variations and clustering is likely in the studied alloy.

Bandwidth Control and Symmetry Breaking in a Mott‐Hubbard Correlated Metal

AbstractIn Mott materials strong electron correlation yields a spectrum of complex electronic structures. Recent synthesis advancements open realistic opportunities for harnessing Mott physics to design transformative devices. However, a major bottleneck in realizing such devices remains the lack of control over the electron correlation strength. This stems from the complexity of the electronic structure, which often veils the basic mechanisms underlying the correlation strength. This study presents control of the correlation strength by tuning the degree of orbital overlap using picometer‐scale lattice engineering. This study illustrates how bandwidth control and concurrent symmetry breaking can govern the electronic structure of a correlated SrVO3 model system. This study shows how tensile and compressive biaxial strain oppositely affect the SrVO3 in‐plane and out‐of‐plane orbital occupancy, resulting in the partial alleviation of the orbital degeneracy. The spectral weight redistribution under strain is derived and explained, which illustrates how high tensile strain drives the system toward a Mott insulating state. Implementation of such concepts can push correlated electron phenomena closer toward new solid‐state devices and circuits. These findings therefore pave the way for understanding and controlling electron correlation in a broad range of functional materials, driving this powerful resource for novel electronics closer toward practical realization.