Change In Electronic Configuration Research Articles

Structural stability of coplanar 1T-2H superlattice MoS2 under high energy electron beam

Coplanar heterojunctions composed of van der Waals layered materials with different structural polymorphs have drawn immense interest recently due to low contact resistance and high carrier injection rate owing to low Schottky barrier height. Present research has largely focused on efficient exfoliation of these layered materials and their restacking to achieve better performances. We present here a microwave assisted easy, fast and efficient route to induce high concentration of metallic 1T phase in the original 2H matrix of exfoliated MoS2 layers and thus facilitating the formation of a 1T-2H coplanar superlattice phase. High resolution transmission electron microscopy (HRTEM) investigations reveal formation of highly crystalline 1T-2H hybridized structure with sharp interface and disclose the evidence of surface ripplocations within the same exfoliated layer of MoS2. In this work, the structural stability of 1T-2H superlattice phase during HRTEM measurements under an electron beam of energy 300 keV is reported. This structural stability could be either associated to the change in electronic configuration due to induction of the restacked hybridized phase with 1T- and 2H-regions or to the formation of the surface ripplocations. Surface ripplocations can act as an additional source of scattering centers to the electron beam and also it is possible that a pulse train of propagating ripplocations can sweep out the defects via interaction from specific areas of MoS2 sheets.

Confined beryllium atom electronic structure and physicochemical properties

Confined beryllium atom ground and first excited states electronic structures are calculated by the direct variational method, taking into account the system asymmetric nature of the trial wave function, adding a cutoff function to ensure confinement boundary conditions. The trial wave function is built up from hydrogenic functions, which constitute an adequate basis for energies calculation. Physicochemical properties such as kinetic energy, pressure, and polarizability are also calculated from energy results previously obtained to different confined radii. Using different variational parameters in each hydrogenic function, the energy approximation obtained is improved. Electronic configuration changes as we move toward the strong confinement region (small cavity radii) in function of its atomic number using impenetrable walls, this region was obtained for Z = 4. This is a conclusion of this work. Another important result is that this method is computationally simpler and gives values inside the experimental precision. Aforementioned results are compared with other theoretical publications.

Type I antiferromagnetic order in Ba2LuReO6: Exploring the role of structural distortions in double perovskites containing 5d2 ions

The structural, electrical, and magnetic properties of the double perovskite Ba2LuReO6 have been examined. It is an insulator whose temperature dependent conductivity is consistent with variable range hopping electrical transport. A transition to an antiferromagnet state with type I order occurs below TN = 31K. High resolution time-of-flight neutron powder diffraction measurements show that it retains the cubic double perovskite structure down to 10K. High intensity, low resolution neutron powder diffraction measurements confirm the antiferromagnetic order and indicate that cubic symmetry is still observed at 1.5K. The small ordered moment of 0.34(4)μB per Re is comparable to estimates of moments on 5d2 ions in other antiferromagnetically ordered cubic double perovskites. Comparisons with related double perovskites containing 5d2 ions, such as Os6+ and Re5+, reveal that subtle changes in structure or electron configuration of the diamagnetic octahedral cations can have a large impact on the magnetic ground state, the size of the ordered moment, and the Néel temperature.

Ultrafast Excited State Relaxation of a Metalloporphyrin Revealed by Femtosecond X-ray Absorption Spectroscopy.

Photoexcited Nickel(II) tetramesitylporphyrin (NiTMP), like many open-shell metalloporphyrins, relaxes rapidly through multiple electronic states following an initial porphyrin-based excitation, some involving metal centered electronic configuration changes that could be harnessed catalytically before excited state relaxation. While a NiTMP excited state present at 100 ps was previously identified by X-ray transient absorption (XTA) spectroscopy at a synchrotron source as a relaxed (d,d) state, the lowest energy excited state (J. Am. Chem. Soc., 2007, 129, 9616 and Chem. Sci., 2010, 1, 642), structural dynamics before thermalization were not resolved due to the ∼100 ps duration of the available X-ray probe pulse. Using the femtosecond (fs) X-ray pulses of the Linac Coherent Light Source (LCLS), the Ni center electronic configuration from the initial excited state to the relaxed (d,d) state has been obtained via ultrafast Ni K-edge XANES (X-ray absorption near edge structure) on a time scale from hundreds of femtoseconds to 100 ps. This enabled the identification of a short-lived Ni(I) species aided by time-dependent density functional theory (TDDFT) methods. Computed electronic and nuclear structure for critical excited electronic states in the relaxation pathway characterize the dependence of the complex's geometry on the electron occupation of the 3d orbitals. Calculated XANES transitions for these excited states assign a short-lived transient signal to the spectroscopic signature of the Ni(I) species, resulting from intramolecular charge transfer on a time scale that has eluded previous synchrotron studies. These combined results enable us to examine the excited state structural dynamics of NiTMP prior to thermal relaxation and to capture intermediates of potential photocatalytic significance.

Investigation of Fluorophosphate Cathode Materials for Na Ion Batteries By Ex Situ 23 Na Solid-State Nuclear Magnetic Resonance

Sodium ion batteries have experienced a renaissance in recent years owing to the low cost and high abundance of sodium relative to lithium resources.1 Despite this renewed attention, there remains a need to realize sodium electrode materials that are suitable for commercial applications. In light of this, there is significant motivation to identify and analyze various properties of novel electrode materials, including structural and ion diffusion changes that occur during the electrochemical cycling process. Solid-state nuclear magnetic resonance (ssNMR) is implemented here in an attempt to characterize structure and site-specific ion mobility in the fluorophosphate family of cathode materials (Na2MPO4F), as they are known to exhibit high thermal and electrochemical stability.2,3 Ex situ 23Na NMR studies at fast magic angle spinning (65 kHz) allow for sufficient spectral resolution to observe local changes at unique Na environments in these paramagnetic electrode materials. Na atoms housed in the two crystallographically unique positions in the layered Na2FePO4F phase are distinguishable via this technique (Figure 1a), offering the opportunity to probe local properties in the pristine phase. Further, by incorporation of this material into a sodium ion cell, the changes to the 23Na NMR spectrum can be correlated ex situ to structural changes directly resulting from the electrochemical (de)intercalation process. The appearance and relative increase of two new Na peaks in the NMR spectrum (Figure 1b) upon electrochemical desodiation of the material suggests that Na atoms in both crystallographic environments may in fact be mobile despite an apparent lack of chemical exchange between sites. These new Na resonances can be assigned to the partially oxidized variant of the pristine material, where the dramatic shift in peaks in the NMR spectrum is attributed to the change in electron configuration of the transition metal from Fe2+ to Fe3+. Ongoing efforts to quantify the diffusion of Na ions and characterize the mechanism of electrochemical desodiation will be presented.

Pressure-induced structural and magnetic transitions in the infinite-chains iron oxide Sr2FeO3: a first-principle investigation

The pressure-induced transition of Sr2FeO3 was studied by first-principle calculation using density functional theory with the generalized gradient approximation plus on-site coulomb repulsion method. It shows that Sr2FeO3 exhibits a structure transition from Immm to Ammm and at about 35 GPa and then a spin transition from high spin S = 2 to intermediate spin S = 1. And it is also revealed that the pressure leads to a change in the Fe three-dimensional electronic configuration from ()1()1()1()1()1 ()1 under ambient conditions to ()1()1()1()1 ()δ()1 ()σ at high pressure, where δ plus σ equals 1.

Oxidation of Electron Donor-Substituted Verdazyls: Building Blocks for Molecular Switches.

Species that can undergo changes in electronic configuration as a result of an external stimulus such as pH or solvent polarity can play an important role in sensors, conducting polymers, and molecular switches. One way to achieve such structures is to couple two redox-active fragments, where the redox activity of one of them is strongly dependent upon environment. We report on two new verdazyls, one subsituted with a di-tert-butyl phenol group and the other with a dimethylaminophenyl group, that have the potential for such behavior upon oxidation. Oxidation of both verdazyls with copper(II) triflate in acetonitrile gives diamagnetic verdazylium ions characterized by NMR and UV-vis spectroscopies. Deprotonation of the phenol-verdazylium results in electron transfer and a switch from a singlet state to a paramagnetic triplet diradical identified by electron spin resonance. The dimethylaminoverdazylium 9 has a diamagnetic ground state, in line with predictions from simple empirical methods and supported by density functional theory calculations. These results indicate that verdazyls may complement nitroxides as spin carriers in the design of organic molecular electronics.

Ferromagnetism of Single-Crystalline Cu2O Induced through Poly(N-vinyl-2-pyrrolidone) Interaction Triggering d-Orbital Alteration

Ferromagnetic-like properties of cuprous oxide (Cu2O) are induced through its interaction with chemisorbed surfactant poly(N-vinyl-2-pyrrolidone) (PVP), which alters the intrinsic d10 configuration of Cu ions. Structural and magnetism-related properties of intact Cu2O crystals (i-Cu2O) and those capped with PVP (c-Cu2O) were examined using various analytical instruments. SEM, TEM (corresponding selected area electron diffraction (SAED)), and XRD of i-Cu2O and c-Cu2O showed cubic and hexagonal shapes of single crystallinity with facets of {200} and {111}, respectively, resulting from the differential growth rates of the original identical crystals along the facets over time. Bulk magnetic susceptibility (χ) of i-Cu2O and c-Cu2O at room temperature in field-dependent magnetization and the difference in their magnetic moment in temperature-dependent magnetization showed diamagnetic and ferromagnetic properties, respectively. The difference in the fluorescence mode of X-ray absorption near edge structure (XANES) spectra between i-Cu2O and c-Cu2O, showing no quadruple pre-edge peak for the transition 1s → 3d in Cu(II) ions with d9 electronic configuration, indicates an orbital alteration on the surface of c-Cu2O caused by an interaction with PVP. Two peaks for c-Cu2O at higher binding energies in O 1s X-ray photoelectron spectroscopy may be indicative of the ligand-to-metal charge transfer (LMCT) from O atoms of PVP to Cu ions of Cu2O, generating a chemical interaction through coordination bonding. Large hyperfine splitting constants in electron paramagnetic resonance (EPR) spectra of c-Cu2O support this interpretation, with septet hyperfine splitting suggestive of Cu–Cu interactions on the surface of c-Cu2O via the interaction with O atoms of PVP. These results demonstrate that PVP capping of Cu2O crystal (c-Cu2O) induces ferromagnetism of Cu(I) ions through coordination with O atoms of chemically adsorbed PVP. This may induce LMCT and Cu–Cu interactions that lead to changes in electronic configurations, deriving the ferromagnetic moments of c-Cu2O.

Square-planar ruthenium(II) complexes: control of spin state by pincer ligand functionalization.

Functionalization of the PNP pincer ligand backbone allows for a comparison of the dialkyl amido, vinyl alkyl amido, and divinyl amido ruthenium(II) pincer complex series [RuCl{N(CH2 CH2 PtBu2 )2 }], [RuCl{N(CHCHPtBu2 )(CH2 CH2 PtBu2 )}], and [RuCl{N(CHCHPtBu2 )2 }], in which the ruthenium(II) ions are in the extremely rare square-planar coordination geometry. Whereas the dialkylamido complex adopts an electronic singlet (S=0) ground state and energetically low-lying triplet (S=1) state, the vinyl alkyl amido and the divinyl amido complexes exhibit unusual triplet (S=1) ground states as confirmed by experimental and computational examination. However, essentially non-magnetic ground states arise for the two intermediate-spin complexes owing to unusually large zero-field splitting (D>+200 cm(-1) ). The change in ground state electronic configuration is attributed to tailored pincer ligand-to-metal π-donation within the PNP ligand series.

A new series of fluorescent indicators for super acids.

The photophysical properties of fluorescent Hammett acidity indicator derived from 3,4,5,6-tetrahydrobis(pyrido[3,2-g]indolo)[2,3-a:3',2'-j]acridine (1a), 6-bis(pyrido[3,2-g]indol-2'-yl)pyridine (1b) and their analogues have been investigated in sulfuric acid solutions by means of absorption, fluorimetry, relaxation dynamics and computational approach. These new indicators undergo a reversible protonation process in the Hammett acidity range of H0 < 0, accompanied by a drastic increase of the bright blue-green (1a) or yellow (1b) fluorescence intensity upon increasing the acidity. For 1a in H2 SO4 , the emission yield increases as large as 200 folds from pH = -0.41 to the Hammett acidity range of -5.17, the results of which are rationalized by a much increase of the steric hindrance upon third protonation toward the central pyridinic site, together with their accompanied changes of electronic configuration from charge transfer to a delocalized ππ* character in the lowest lying excited state. The combination of 1a and 1b renders a wide and linear range of H0 measurement from -1.2 to -5.1 detected by highly intensive fluorescence.

An organic spin crossover material in water from a covalently linked radical dyad.

A covalently linked viologen radical cation dyad acts as a reversible thermomagnetic switch in water. Cycling between diamagnetic and paramagnetic forms by heating and cooling is accompanied by changes in optical and magnetic properties with high radical fidelity. Thermomagnetic switches in water may eventually find use as novel biological thermometers and in temperature-responsive organic materials where the changes in properties originate from a change in electronic spin configuration rather than a change in structure.

Optimal Composition of Atomic Orbital Basis Sets for Recovering Static Correlation Energies

Static correlation energies (Estat) are calculated in a range of basis sets for a chemically diverse collection of atoms and molecules. The reliability of a basis set in capturing Estat is assessed according to the following: mean and maximum absolute deviations from near-exact Estat estimates, monotonic convergence to the complete basis set limit, and ability to capture Estat accurately independent of changes in geometry, molecular size, and electronic configuration. Within the polarization and correlation-consistent basis set series, triple-ζ basis sets are the smallest that can reliably capture Estat. The cc-pVTZ basis set performs particularly well, recovering Estat to chemical accuracy for all atoms and molecules in our data set. A series of customized basis sets are constructed by stripping polarization functions from, and swapping polarization functions among, existing basis sets. Basis sets without polarization functions are incapable of accurately recovering Estat. Basis sets with a near-complete set of s, p, and d functions can approach chemical accuracy in maximum absolute error. However, this may be achieved at lower computational cost by using a well balanced triple-ζ basis set including f functions, along with a smaller number of s, p, and d functions. Recommended basis sets for calculating Estat with increasing accuracy at increasing computational cost are 6-311G(2d,2p), cc-pVTZ, and cc-pVQZ stripped of g functions.

Electronic Structures and Magnetism of SrFeO2 under Pressure: A First-Principles Study

We have studied the electronic structures and magnetism of SrFeO2 under pressure by first-principles calculations in the framework of density functional theory (DFT) with GGA+U and HSE06 hybrid functionals, respectively. The pressure-induced spin transition from S = 2 to S = 1 and the antiferromagnetic-ferromagnetic (AFM-FM) transition observed in experiment are well reproduced by taking the site repulsion U and its pressure dependence into account. The electronic structure and its change with the pressure can be qualitatively understood in an ionic model together with the hybridization effects between the Fe 3d and O 2p states. It is found that the pressure leads to a change in Fe 3d electronic configuration from (d(z(2)))(2)(d(xz)d(yz))(2)(d(xy))(1)(d(x(2)-y(2)))(1) under ambient conditions to (d(z(2)))(2)(d(xz)d(yz))(3)(d(xy))(1)(d(x(2)-y(2)))(0) at high pressure. As a result, the spin state transits from S = 2 to S = 1 and both the antiferromagnetic intralayer Fe-O-Fe superexchange interaction and the interlayer Fe-Fe direction exchange coupling at ambient pressure become ferromagnetic at high pressure according to the Goodenough-Kanamori (G-K) rules. Additionally, our calculations predict another spin transition from S = 1 to S = 0 at pressures of about 220 GPa.

Effect of rare earth substitution in the density of electronic states of LnOFeAs

Measurements of the Fe K-edge x-ray absorption near edge (XANES) spectra of LnOFeAs (Ln being a lanthanide) high Tc superconductors exhibit significant changes in the pre-edge peak region upon rare earth substitution. Ab initio XANES calculations, based on the local structure centered at the Fe site obtained by crystallographic investigations, reproduce the observed changes in the spectra, indicating variations of the Fe d-local unoccupied electronic states. The calculated Fe density of states (DOS) at the Fermi energy shows an increase of the Fe d-density of states with increasing height of the arsenic atomic position with respect to the iron plane, similar to that observed for the superconducting transition temperature, Tc. These calculations show that not only the atomic position variation of the Fe-As layers induced by the rare earth substitution is relevant in the increase of the DOS at the Fermi-level, but the actual change in electronic configuration of the rare earth also plays a role in the increase of Fe d-density of states at the Fermi energy.

Experimental design of control strategy based on brake pressure changes on wet and slippery surfaces of rough road for variable damper setting during braking with activated anti-lock brake system

In this study, the control strategy based on experimental study is established for a variable damper setting with activated anti-lock brake system. For this, anti-lock brake system braking tests have been conducted by using hard, medium–hard and soft dampers on a rough road which has wet and slippery surfaces. In anti-lock brake system tests, brake pressure has been measured. The brake pressure increasing and decreasing rates have been obtained using measured brake pressure. The control strategy has been designed by using threshold values acquired from these test results related to brake pressure. For this, firstly, the brake pressure change thresholds of damper providing the shortest braking distance are determined. Then, the damping capacity stage rules are designed by depending on the brake pressure thresholds corresponding to the road conditions. The control strategy performance has been evaluated during transitions between wet and slippery roads. The results show that this control strategy is effectively applied to passenger cars without any change in electronic control unit configuration of anti-lock brake system. For this control strategy, it is considerably important that the damper setting to provide the shortest braking distance is detected.

Raman scattering characterization of a carbon coating after low-energy argon ion bombardment

The characteristic of Raman scattering spectra of a carbon coating, which was modified by radio frequency argon plasma, has been investigated. The argon ion bombardment causes changes in the microstructure and amount of stress in the coating. Raman scattering spectra are discussed in terms of intensity, bandwidth and wavenumber. The evolvement of Raman spectra shows the following behavior with increasing bombardment time: the intensity changes of the disordered D band, amorphous D ″ band and graphite G band could be separated into several stages; low-energy argon ion bombardment over a short period can reduce the number of defects in the carbon coating, while a larger bombardment period can increase the number of defects; the widths of the D and G bands both increase, while that of the D ″ band decreases; the wavenumbers of all the three bands fluctuate according to the changes in electronic configuration and amount of stress in the carbon coating.

Concerted electron-proton transfer in the optical excitation of hydrogen-bonded dyes

The simultaneous, concerted transfer of electrons and protons--electron-proton transfer (EPT)--is an important mechanism utilized in chemistry and biology to avoid high energy intermediates. There are many examples of thermally activated EPT in ground-state reactions and in excited states following photoexcitation and thermal relaxation. Here we report application of ultrafast excitation with absorption and Raman monitoring to detect a photochemically driven EPT process (photo-EPT). In this process, both electrons and protons are transferred during the absorption of a photon. Photo-EPT is induced by intramolecular charge-transfer (ICT) excitation of hydrogen-bonded-base adducts with either a coumarin dye or 4-nitro-4'-biphenylphenol. Femtosecond transient absorption spectral measurements following ICT excitation reveal the appearance of two spectroscopically distinct states having different dynamical signatures. One of these states corresponds to a conventional ICT excited state in which the transferring H(+) is initially associated with the proton donor. Proton transfer to the base (B) then occurs on the picosecond time scale. The other state is an ICT-EPT photoproduct. Upon excitation it forms initially in the nuclear configuration of the ground state by application of the Franck-Condon principle. However, due to the change in electronic configuration induced by the transition, excitation is accompanied by proton transfer with the protonated base formed with a highly elongated (+)H ─ B bond. Coherent Raman spectroscopy confirms the presence of a vibrational mode corresponding to the protonated base in the optically prepared state.

Electron density distribution in vanadium and niobium fromγ-ray diffraction

The electron density distribution in paramagnetic vanadium and niobium is derived via multipole refinement of high-quality single-crystal diffraction data, complete up to sin\ensuremath{\theta}/\ensuremath{\lambda} $=$ 1.9 \AA{}${}^{\ensuremath{-}1}$, collected at room temperature with 316.5 keV $\ensuremath{\gamma}$ radiation. Four $\ensuremath{\gamma}$ lines in the energy range 200--600 keV have been used to extrapolate extinction-free low-order structure factors. Both metals display charge asphericity due to preferential occupancy of the ${t}_{2g}$ orbital. The asphericity in V is in quantitative agreement with ab initio calculations, but not with earlier experimental results, laying at rest a long-standing debate. In both metals, the $d$-electron density is strongly contracted relative to the free atoms. The high-precision thermal parameters are in good agreement with some of the older results. No support is found in the data for anharmonic contributions to the thermal parameters, contrary to claims in previous reports on V. Attention is paid to the 3$d$-4$s$ occupation problem in V, indicating no change in electronic configuration between atom and metal. Relativistic form factor issues are also discussed. It is pointed out that for the analysis of crystallographic data nonrelativistic form factors are to be preferred over their relativistic counterparts.

Carboxylate Shifts Steer Interquinone Electron Transfer in Photosynthesis

Understanding the mechanisms of electron transfer (ET) in photosynthetic reaction centers (RCs) may inspire novel catalysts for sunlight-driven fuel production. The electron exit pathway of type II RCs comprises two quinone molecules working in series and in between a non-heme iron atom with a carboxyl ligand (bicarbonate in photosystem II (PSII), glutamate in bacterial RCs). For decades, the functional role of the iron has remained enigmatic. We tracked the iron site using microsecond-resolution x-ray absorption spectroscopy after laser-flash excitation of PSII. After formation of the reduced primary quinone, Q(A)(-), the x-ray spectral changes revealed a transition (t½ ≈ 150 μs) from a bidentate to a monodentate coordination of the bicarbonate at the Fe(II) (carboxylate shift), which reverted concomitantly with the slower ET to the secondary quinone Q(B). A redox change of the iron during the ET was excluded. Density-functional theory calculations corroborated the carboxylate shift both in PSII and bacterial RCs and disclosed underlying changes in electronic configuration. We propose that the iron-carboxyl complex facilitates the first interquinone ET by optimizing charge distribution and hydrogen bonding within the Q(A)FeQ(B) triad for high yield Q(B) reduction. Formation of a specific priming intermediate by nuclear rearrangements, setting the stage for subsequent ET, may be a common motif in reactions of biological redox cofactors.

Investigation of the electronic and geometric structures of the (110) surfaces of arsenopyrite (FeAsS) and enargite (Cu3AsS4)

AbstractThe (110) surfaces of arsenopyrite (FeAsS) and enargite (Cu3AsS4) have been modelled using a Density Functional Theory (DFT) plane-wave pseudopotential method (CASTEP) in order to better understand aspects of the geometric and electronic structures of these minerals, which have important implications for the release of arsenic in acid mine drainage environments. In this study, bulk calculations of these minerals have been conducted to give consistent geometries for surface models and to establish reference states for changes at the surfaces in these models. Surface structure experimental data for enargite were collected using low-energy electron diffraction which confirmed an unreconstructed 161 (110) lattice, with a and b values of 6.38±0.3 Å and 9.92±0.5 Å, respectively. Surface calculations demonstrate geometric and electronic relaxation of both arsenopyrite and enargite (110) surfaces. Changes in atomic positions, interatomic distances, Mulliken charges and electronic configurations are reported. Enargite has a surface energy of ∼0.02 eV/Å2 compared with arsenopyrite which has a surface energy of ∼0.11 eV/Å2, indicating that the enargite (110) surface is more energetically stable than that of arsenopyrite. The most stable surfaces are those which relax to restore the surface coordination and partial charge balance. For both minerals this is achieved by the formation of covalent bonds. Arsenic has the most positive Mulliken charge of all the surface atoms and is, therefore, predicted to be the most reactive atom at the arsenopyrite and enargite (110) surfaces. This implies that, according to these calculations, arsenic is most likely to react with oxidative species such as O2 and H2O in environments such as those associated with acid mine drainage, potentially releasing oxides and acids of arsenic into the environment.