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Valence-to-core X-ray emission spectroscopy to resolve the size-dependent valence electronic structure of Pt nanoparticles
X-ray characterization of catalyst materials using synchrotron radiation has become more widely available to the scientific community in recent decades.
Quantitative first-principles calculations of valence and core excitation spectra of solid C 60
Not Available
Microscopic theory of the nearest-neighbor valence bond sector of the spin- 1 2 kagome antiferromagnet
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Ultrafast Charge Transfer of a Valence Double Hole in Glycine Driven Exclusively by Nuclear Motion
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Rechargeable Solid-State Copper Sulfide Cathodes for Alkaline Batteries: Importance of the Copper Valence State.
Abstract not provided.
Pauling’s rules for oxide-based minerals: A re-examination based on quantum mechanical constraints and modern applications of bond-valence theory to Earth materials
Since their introduction in 1929, Pauling’s five rules have been used by scientists from many disciplines to rationalize and predict stable arrangements of atoms and coordination polyhedra in crystalline solids; amorphous materials such as silicate glasses and melts; nanomaterials, poorly crystalline solids; aqueous cation and anion complexes; and sorption complexes at mineral-aqueous solution interfaces. The predictive power of these simple yet powerful rules was challenged recently by George et al. (2020), who performed a statistical analysis of the performance of Pauling’s five rules for about 5000 oxide crystal structures. They concluded that only 13% of the oxides satisfy the last four rules simultaneously and that the second rule has the most exceptions. They also found that Pauling’s first rule is satisfied for only 66% of the coordination environments tested and concluded that no simple rule linking ionic radius to coordination environment will be predictive due to the variable quality of univalent radii. We address these concerns and discuss quantum mechanical calculations that complement Pauling’s rules, particularly his first (radius sum and radius ratio rule) and second (electrostatic valence rule) rules. We also present a more realistic view of the bonded radii of atoms, derived by determining the local minimum in the electron density distribution measured along trajectories between bonded atoms known as bond paths, i.e., the bond critical point (rc). Electron density at the bond critical point is a quantum mechanical observable that correlates well with Pauling bond strength. Moreover, a metal atom in a polyhedron has as many bonded radii as it has bonded interactions, resulting in metal and O atoms that may not be spherical. O atoms, for example, are not spherical in many oxide-based crystal structures. Instead, the electron density of a bonded oxygen is often highly distorted or polarized, with its bonded radius decreasing systematically from ~1.38 Å when bonded to highly electropositive atoms like sodium to 0.64 Å when bonded to highly electronegative atoms like nitrogen. Bonded radii determined for metal atoms match the Shannon (1976) radii for more electropositive atoms, but the match decreases systematically as the electronegativities of the M atoms increase. As a result, significant departures from the radius ratio rule in the analysis by George et al. (2020) is not surprising. We offer a modified, more fundamental version of Pauling’s first rule and demonstrate that the second rule has a one-to-one connection between the electron density accumulated between the bonded atoms at the bond critical point and the Pauling bond strength of the bonded interaction. Pauling’s second rule implicitly assumes that bond strength is invariant with bond length for a given pair of bonded atoms. Many studies have since shown that this is not the case, and Brown and Shannon (1973) developed an equation and a set of parameters to describe the relation between bond length and bond strength, now redefined as bond valence to avoid confusion with Pauling bond-strength. Brown (1980) used the valence-sum rule, together with the path rule and the valence-matching principle, as the three axioms of bond-valence theory (BVT), a powerful method for understanding many otherwise elusive aspects of crystals and also their participation in dynamic processes. We show how a priori bond-valence calculations can predict unstrained bond-lengths and how bond-valence mapping can locate low-Z atoms in a crystal structure (e.g., Li) or examine possible diffusion pathways for atoms through crystal structures. In addition, we briefly discuss Pauling’s third, fourth, and fifth rules, the first two of which concern the sharing of polyhedron elements (edges and faces) and the common instability associated with structures in which a polyhedron shares an edge or face with another polyhedron and contains high-valence cations. The olivine [α-(MgxFe1–x)2SiO4] crystal structure is used to illustrate the distortions from hexagonal close-packing of O atoms caused by metal-metal repulsion across shared polyhedron edges. We conclude by discussing several applications of BVT to Earth materials, including the use of BVT to: (1) locate H+ ions in crystal structures, including the location of protons in the crystal structures of nominally anhydrous minerals in Earth’s mantle; (2) determine how strongly bonded (usually anionic) structural units interact with weakly bonded (usually cationic) interstitial complexes in complex uranyl-oxide and uranyl-oxysalt minerals using the valence-matching principle; (3) calculate Lewis acid strengths of cations and Lewis base strengths of anions; (4) determine how (H2O) groups can function as bond-valence transformers by dividing one bond into two bonds of half the bond valence; (5) help characterize products of sorption reactions of aqueous cations (e.g., Co2+ and Pb2+) and oxyanions [e.g., selenate (Se6+O4)2- and selenite (Se4+O3)2-] at mineral-aqueous solution interfaces and the important role of protons in these reactions; and (6) help characterize the local coordination environments of highly charged cations (e.g., Zr4+, Ti4+, U4+, U5+, and U6+) in silicate glasses and melts.
The photocatalytic performance of Ta and Rh co-doped TiO2 tuned by the average dopant valence
Highlights: • Effects of dopant valence on the photocatalytic performance was investigated. • New strategy was worked out to investigate effects of dopant valence. • The dopant valence was changed but the ionic radius keeps constant. • Average valence of Rh and Ta in Ti{sub 0.96}Ta{sub 0.04−x}Rh{sub x}O{sub 2} was changed multiply. • The optimal photocatalyst was obtained as the average valence approaches +4. - Abstract: In order to reveal the effects of dopant average valence on the photocatalytic performance, Ta and Rh co-doped Ti{sub 0.96}Ta{sub 0.04−x}Rh{sub x}O{sub 2} (x = 0, 0.008, 0.016, 0.02, 0.024, 0.032, and 0.04) samples were crystallized at 450 °C and 800 °C, respectively; then the 800 °C crystallized x = 0.02 sample was subsequently reduced in the H{sub 2}/N{sub 2} mixture gases at 600, 700, 800, and 900 °C. Under different processing conditions, Ta remains the valence of +5, while the valence of Rh varies. Rh exhibits Rh{sup 3+} and Rh{sup 4+} in the 450 °C crystallized samples and is completely oxidized to Rh{sup 4+} in the 800 °C crystallized samples. In the reduced samples, Rh exists in the forms of Rh, Rh{sup 3+} and Rh{sup 4+}. The optimal photocatalyst is obtained as the ratio of Rh{sup 3+}/Rh{sup 4+} is 2.11 or the average valence of doped Ta and Rh is closest to the +4 valence of substituted Ti.
Residual mean field model of valence quarks in the nucleon
Abstract We develop a non-perturbative model for valence parton distribution functions (PDFs) based on the mean field interactions of valence quarks in the nucleonic interior. The main motivation for the model is to obtain a mean field description of the valence quarks as a baseline to study the short range quark–quark interactions that generate the high x tail of PDFs. The model is based on the separation of the valence three-quark cluster and residual system in the nucleon. Then the nucleon structure function is calculated within the effective light-front diagrammatic approach introducing nonperturbative light-front valence quark and residual wave functions. Within the model a new relation is obtained between the position, $$x_p$$ x p , of the peak of $$xq_V(x)$$ x q V ( x ) distribution of the valence quark and the effective mass of the residual system, $$m_R$$ m R , in the form: $$x_{p} \approx {1\over 4} (1-{m_R\over m_N})$$ x p ≈ 1 4 ( 1 - m R m N ) at starting $$Q^2$$ Q 2 . This relation explains the difference in the peak positions for d- and u-quarks through the expected difference of residual masses for valence d- and u-quark distributions. The parameters of the model are fixed by fitting the calculated valence quark distributions to the phenomenological PDFs. This allowed us to estimate the overall mean field contribution in baryonic and momentum sum rules for valence d- and u-quarks. Finally, the evaluated parameters of the non-perturbative wave functions of valence 3q-cluster and residual system can be used in calculation of other quantities such as nucleon form factors, generalized partonic and transverse momentum distributions.
Experimental Constraints on the Partitioning and Valence of V and Cr in Garnet and Coexisting Glass
A series of experiments with garnet and coexisting melt have been carried out across a range of oxygen fugacities (near hematite-magnetite (HM) to below the iron-wustite (IW) buffers) at 1.7 GPa to study the partitioning and valence of Cr and V in both phases. Experiments were carried out in a non end loaded piston cylinder apparatus, and the run products were analyzed with electron microprobe and xray absorption near edge structure (XANES) analysis at beamline 13-ID at the Advanced Photon Source of Argonne National Lab. The valence of vanadium and chromium were determined using the position and intensity of the Ka pre-edge peaks, calibrated on a series of Cr and Vbearing standard glasses. This technique has been applied to V and Cr in glasses and V in spinels previously, and in these isotropic phases there are no orientational effects on the XANES spectra (Righter et al., 2006, Amer. Mineral. 91, 1643-1656). We also now demonstrate this to be true for V and Cr in garnet. Also, previous work has shown that V has a higher valence in the glass (or melt) than in the coexisting spinel. This is also true for V in garnet-glass pairs in this study. Vanadium valence in garnets varies from 2.7 below the IW buffer to 3.7 near HM, and for coexisting glass it varies from 3.2 to 4.3. Vanadium valence measured in some natural garnets from mantle localities indicates V in the more reduced range at 2.5. Comparisons will be made between fO2 estimated from V valence and other methods for garnet-bearing mantle samples. In contrast, Cr valence measured in garnet and coexisting glass for all experimental and natural samples is 2.9- 3.0, suggesting that the valence of Cr does not vary within either phase across a large fO2 range. These results demonstrate that while V varies from 2+ to 3+ to 4+ in garnet-melt systems, Cr does not, and this will ultimately affect the partitioning behavior of these two elements in natural systems. Garnet/melt D(Cr) are between 12 and 17 across this range of fO2, whereas D(V) has the highest partition coefficient approx.3, near the IW buffer where the valence of V is almost entirely 3+.
Mixed-valence halide perovskites
Mixed-valence compounds—which feature an element in at least two different oxidation states—can display emergent optical and transport phenomena stemming from electron transfer between the different valences (intervalence charge-transfer; IVCT). As halide perovskites show promise as active materials in numerous optoelectronic devices, it is an opportune moment to incorporate and study the effects of mixed-valence in this versatile materials family, to access tunable electronic structures ranging from insulators to semiconductors to metals. Herein, we introduce the basic concepts of mixed-valence in molecules and discuss how these concepts may be extended to mixed-valence in extended solids. We then review the few studies of mixed valence in 3D and 2D halide perovskites and halide perovskites with mixed-valence impurities, ranging from studies in the early 1900s to the present day. In conclusion, through judicious choice of metal ion, its coordinating ligands and their geometry, and overall structural dimensionality, chemists can exert powerful synthetic control over electronic delocalization in mixed-valence perovskites, and we hope to see this intriguing materials class expand to encompass new compositions.
Diabatic Valence-Hole Concept
A global diabatization scheme, based on the “valence-hole” concept, has been previously applied to model webs of avoided crossings that exist in four electronic-state symmetry manifolds of C 2 ( 1 Π g , 3 Π g , 1 Σ u + , and 3 Σ u + ). Here, this model is extended to the electronically excited states of four more molecules: CN ( 2 Σ + ), N 2 ( 3 Π u ), SiC ( 3 Π), and Si 2 ( 3 Π g ). Many strangenesses in the spectroscopic observations (e.g., energy level structure, predissociation linewidths, and radiative lifetimes) for all four electronic state systems discussed here are accounted for by this unified model. The key concept of the model is valence-hole electron configurations: 3σ 2 4σ 1 1π 4 5σ 2 in CN ( 2 Σ + ), 2σ g 2 2σ u 1 1π u 4 3σ g 2 1π g 1 in N 2 ( 3 Π u ), 5σ 2 6σ 1 7σ 2 2π 3 in SiC ( 3 Π), and 4σ g 2 4σ u 1 5σ g 2 2π u 3 in Si 2 ( 3 Π g ), all of which have a triply occupied “valence-core” (i.e., 2σ g 2 2σ u 1 or the equivalent). These valence-hole configurations have a nominal bond order of three or higher and correlate with high-energy separated-atom limits with an np ← ns (n = 2, 3) promotion in one of the atomic constituents. On its way to dissociation, the strongly bound diabatic valence-hole state crosses multiple weakly bound or repulsive states, which belong to electron configurations with a completely filled valence-core. These curve crossings between diabatic potentials result in a network of many avoided crossings among multiple electronic states, analogous to the well-studied electronic structure landscape of ionic-covalent crossings in strongly ionic molecules. In conclusion, considering the unique role of valence-hole states in shaping the global electronic structure, the valence-hole concept should be added to our intuitive framework of chemical bonding.
Depth-dependent atomic valence determination by synchrotron techniques
The properties of many materials can be strongly affected by the atomic valence of the contained individual elements, which may vary at surfaces and other interfaces. These variations can have a critical impact on material performance in applications. In this work, a non-destructive method for the determination of layer-by-layer atomic valence as a function of material thickness is presented for La 0.7 Sr 0.3 MnO 3 (LSMO) thin films. The method utilizes a combination of bulk- and surface-sensitive X-ray absorption spectroscopy (XAS) detection modes; here, the modes are fluorescence yield and surface-sensitive total electron yield. The weighted-average Mn atomic valence as measured from the two modes are simultaneously fitted using a model for the layer-by-layer variation of valence based on theoretical model Hamiltonian calculations. Using this model, the Mn valence profile in LSMO thin film is extracted and the valence within each layer is determined to within an uncertainty of a few percent. The approach presented here could be used to study the layer-dependent valence in other systems or extended to different properties of materials such as magnetism.
Electrostatic potential and valence modulation in La 0.7 Sr 0.3 MnO 3 thin films
The Mn valence in thin film La 0.7 Sr 0.3 MnO 3 was studied as a function of film thickness in the range of 1–16 unit cells with a combination of non-destructive bulk and surface sensitive X-ray absorption spectroscopy techniques. Using a layer-by-layer valence model, it was found that while the bulk averaged valence hovers around its expected value of 3.3, a significant deviation occurs within several unit cells of the surface and interface. These results were supported by first principles calculations. The surface valence increases to up to Mn 3.7+ , whereas the interface valence reduces down to Mn 2.5+ . The change in valence from the expected bulk value is consistent with charge redistribution due to the polar discontinuity at the film-substrate interface. The comparison with theory employed here illustrates how this layer-by-layer valence evolves with film thickness and allows for a deeper understanding of the microscopic mechanisms at play in this effect. These results offer insight on how the two-dimensional electron gas is created in thin film oxide alloys and how the magnetic ordering is reduced with dimensionality.
Probing ultrafast C–Br bond fission in the UV photochemistry of bromoform with core-to-valence transient absorption spectroscopy
UV pump–extreme UV (XUV) probe femtosecond transient absorption spectroscopy is used to study the 268 nm induced photodissociation dynamics of bromoform (CHBr3). Core-to-valence transitions at the Br(3d) absorption edge (∼70 eV) provide an atomic scale perspective of the reaction, sensitive to changes in the local valence electronic structure, with ultrafast time resolution. The XUV spectra track how the singly occupied molecular orbitals of transient electronic states develop throughout the C–Br bond fission, eventually forming radical Br and CHBr2 products. Complementary ab initio calculations of XUV spectral fingerprints are performed for transient atomic arrangements obtained from sampling excited-state molecular dynamics simulations. C–Br fission along an approximately CS symmetrical reaction pathway leads to a continuous change of electronic orbital characters and atomic arrangements. Two timescales dominate changes in the transient absorption spectra, reflecting the different characteristic motions of the light C and H atoms and the heavy Br atoms. Within the first 40 fs, distortion from C3v symmetry to form a quasiplanar CHBr2 by the displacement of the (light) CH moiety causes significant changes to the valence electronic structure. Displacement of the (heavy) Br atoms is delayed and requires up to ∼300 fs to form separate Br + CHBr2 products. We demonstrate that transitions between the valence-excited (initial) and valence + core-excited (final) state electronic configurations produced by XUV absorption are sensitive to the localization of valence orbitals during bond fission. The change in valence electron-core hole interaction provides a physical explanation for spectral shifts during the process of bond cleavage.
AgI alloying in SnTe boosts the thermoelectric performance via simultaneous valence band convergence and carrier concentration optimization
SnTe, a Pb-free analogue of PbTe, was earlier assumed to be a poor thermoelectric material due to excess p-type carrier concentration and large energy separation between light and heavy hole valence bands. Here, we report the enhancement of the thermoelectric performance of p-type SnTe by Ag and I co-doping. AgI (1–6 mol%) alloying in SnTe modulates its electronic structure by increasing the band gap of SnTe, which results in decrease in the energy separation between its light and heavy hole valence bands, thereby giving rise to valence band convergence. Additionally, iodine doping in the Te sublattice of SnTe decreases the excess p-type carrier concentration. Due to significant decrease in hole concentration and reduction of the energy separation between light and heavy hole valence bands, significant enhancement in Seebeck coefficient was achieved at the temperature range of 600–900 K for Sn{sub 1−x}Ag{sub x}Te{sub 1−x}I{sub x} samples. A maximum thermoelectric figure of merit, zT, of ~1.05 was achieved at 860 K in high quality crystalline ingot of p-type Sn{sub 0.95}Ag{sub 0.05}Te{sub 0.95}I{sub 0.05}. - Graphical abstract: Significant decrease in hole concentration and reduction of the energy separation between light and heavy hole valence bands resulted in a maximum thermoelectric figure of merit, zT, of ~1.05 at 860 K in high quality crystalline ingot of p-type Sn{sub 0.95}Ag{sub 0.05}Te{sub 0.95}I{sub 0.05}. - Highlights: • AgI alloying in SnTe increases the principle band gap. • Hole concentration reduction and valence band convergence enhances thermopower of SnTe-AgI. • A maximum zT of ~1.05 was achieved at 860 K in p-type Sn{sub 0.95}Ag{sub 0.05}Te{sub 0.95}I{sub 0.05}.
Charge and Spin-State Characterization of Cobalt Bis( o -dioxolene) Valence Tautomers Using Co Kβ X-ray Emission and L-Edge X-ray Absorption Spectroscopies
The valence tautomeric states of Co(phen)(3,5-DBQ) 2 and Co(tmeda)(3,5-DBQ) 2 , where 3,5-DBQ is either the semiquinone (SQ – ) or catecholate (Cat 2– ) form of 3,5-di- tert -butyl-1,2-benzoquinone, have been examined by a series of cobalt-specific X-ray spectroscopies. In this work, we have utilized the sensitivity of 1s3p X-ray emission spectroscopy (Kβ XES) to the oxidation and spin states of 3d transition-metal ions to determine the cobalt-specific electronic structure of valence tautomers. A comparison of their Kβ XES spectra with the spectra of cobalt coordination complexes with known oxidation and spin states demonstrates that the low-temperature valence tautomer can be described as a low-spin Co III configuration and the high-temperature valence tautomer as a high-spin Co II configuration. This conclusion is further supported by Co L-edge X-ray absorption spectroscopy (L-edge XAS) of the high-temperature valence tautomers and ligand-field atomic-multiplet calculations of the Kβ XES and L-edge XAS spectra. In conclusion, the nature and strength of the magnetic exchange interaction between the cobalt center and SQ – in cobalt valence tautomers is discussed in view of the effective spin at the Co site from Kβ XES and the molecular spin moment from magnetic susceptibility measurements.