Polycrystalline samples of ternary rare earth germanides R$_{2}$Co$_{3}$Ge$_{5}$(R = La, Ce and Pr) have been prepared and investigated by means of magnetic susceptibility, isothermal magnetization, electrical resistivity and specific heat measurements. All these compounds crystallize in orthorhombic U$_{2}$Co$_{3}$Si$_{5}$ structure (space group \textit{Ibam}). No evidence of magnetic or superconducting transition is observed in any of these compounds down to 2 K. The unit cell volume of Ce$_{2}$Co$_{3}$Ge$_{5}$ deviates from the expected lanthanide contraction, indicating non trivalent state of Ce ions in this compound. The reduced value of effective moment ($μ_{eff}$ $\approx$ 0.95 $μ_{B}$) compared to that expected for trivalent Ce ions further supports valence fluctuating nature of Ce in Ce$_{2}$Co$_{3}$Ge$_{5}$. The observed temperature dependence of magnetic susceptibility is consistent with ionic interconfiguration fluctuation (ICF) model. Although no sharp anomaly due to a phase transition is seen, a broad Schottky-type anomaly is observed in the magnetic part of specific heat of Pr$_{2}$Co$_{3}$Ge$_{5}$. An analysis of $C_{mag}$ data suggests a singlet ground state in Pr$_{2}$Co$_{3}$Ge$_{5}$ separated from the singlet first excited state by 22 K and a doublet second excited state at 73 K.
The valence band offsets (VBO) for the \b{eta}-type A3B6 layered compounds depending on the thickness of the crystals have been investigated from the first principles, based on the density functional theory. To simulate the structure of a given thickness the periodic slab model was used. Two adjacent crystal slabs consisting of several layers were separated by a vacuum region of two-layer width. It is shown that at the crystal thickness more than 12 layers, photothreshold practically becomes independent on the thickness of the crystal.
We have applied the bond valence method to cerium oxides to determine the oxidation states of the Ce ion at the various site symmetries of the crystals. The crystals studied include cerium dioxide and the two sesquioxides along with some selected intermediate phases which are crystallographically well characterized. Our results indicate that cerium dioxide has a mixed-valence ground state with an f-electron population on the Ce site of 0.27 while both the A- and C-sesquioxides have a nearly pure f^1 configuration. The Ce sites in most of the intermediate oxides have non-integral valences. Furt…
We report on simple experiment on temperature-dependent Hall effect measurements in GaMnAs single crystalline samples with Mn composition estimated at 0.05-0.3 at.% which is slightly below the onset of ferromagnetism. Impurity band transport is visible for Mn compositions of ~0.3 at.% as a clear metallic behaviour. The results show interesting situation that the Metal-Insulator transition in GaAs:Mn occurs within the impurity band which is separated from the valence bands for Mn concentrations studied here. We also discuss on the equilibrium high temperature solubility limit of Mn in GaAs, unk…
High quality single crystals of Cs$_2$Au$_2$X$_6$ (X=Br,I) were grown using a ternary self-flux method. Structural refinements based on single crystal X-ray diffraction measurements show that both materials have a distorted perovskite structure belonging to the I4/mmm space group with full site occupancy. Transport measurements reveal a large bandgap of 550 $\pm$ 100 meV for Cs$_2$Au$_2$I$_6$ and 520 $\pm$ 80 meV for Cs$_2$Au$_2$Br$_6$. Initial attempts at chemical substitution are described.
In their paper [Opt. Mater. 24, 333, 2003], Feldman et al conducted an experimental study of the dynamics of chromium ion valence transformations in Cr,Ca:YAG crystals among the trivalent Cr3+ state, and two tetravalent Cr4+ ones, of octahedral and tetrahedral coordination. The temperatures used ranged between ~800 and 1,000 C. The basic effects are the transition of Cr3+ into Cr4+ under high-temperature annealing in an oxidizing atmosphere, and the reverse transition under a reducing atmosphere, or in vacuum. In the present theory, we interpret the processes by oxygen-vacancy diffusion in the…
The electronic structure of the cleaved perovskite (CH3NH3PbBr3) single crystal was studied in an ultra-high vacuum (UHV) system by angle-resolved photoemission spectroscopy (ARPES) and inverse photoelectron spectroscopy (IPES). Highly reproducible dispersive features of the valence bands were observed with nice symmetry about the Brillouin zone center and boundaries. The largest dispersion width was found to be ~0.73 eV and ~0.98 eV along the ΓX and ΓM directions, respectively. The effective mass of the holes was estimated to be ~0.59 m0. The quality of the surface was verified by atomic forc…
Using a valence force field model based on that introduced by Martin, we present three related methods through which we analytically determine valence force field parameters. The methods introduced allow easy derivation of valence force field parameters in terms of the Kleinman parameter $ζ$ and bulk properties of zincblende and diamond crystals. We start with a model suited for covalent and weakly ionic materials, where the valence force field parameters are derived in terms of $ζ$ and the bulk elastic constants $C_{11}$, $C_{12}$, and $C_{44}$. We show that this model breaks down as the mate…
Suppression of the valence transition in solution-grown single crystals of Eu$_2$Pt$_6$Al$_{15}$
Iowa State University（爱荷华州立大学）；Ames National Laboratory（艾姆斯国家实验室）；McGill University（麦吉尔大学）；Universität des Saarlandes（萨尔兰州立大学）；Universität Münster（明斯特大学）；University of Sao Paulo（圣保罗大学）
Progress of theories and experiments of the quantum valence criticality is overviewed focusing on recent discoveries of direct evidence of quantum critical point of valence transitions in periodic crystal $α$-YbAl$_{1-x}$Fe$_x$B$_4$ at $x=0.014$ and quasicrystal Yb$_{15}$(Al$_{1-x} $Ga$_{x}$)$_{34}$(Au$_{1-y}$Cu$_{y}$)$_{51}$ at $x=y=0$. The common quantum criticality as well as $T/B$ scaling behavior in the magnetization observed in the periodic crystal $β$-YbAlB$_4$ and quasicrystal Yb$_{15}$Al$_{34}$Au$_{51}$ is shown to be explained from the theory of critical Yb-valence fluctuations start…
The valence fluctuations which are related to the charge disproportionation of phosphorous ions $P^{4+} + P^{4+}\rightarrow P^{3+} + P^{5+}$ are the origin of ferroelectric and quantum paraelectric states in Sn(Pb)$_2$P$_2$S$_6$ semiconductors. They involve recharging of SnPS$_3$ or PbPS$_3$ structural groups which could be represented as half-filled sites in the crystal lattice. Temperature-pressure phase diagram for Sn$_2$P$_2$S$_6$ compound and temperature-composition phase diagram for (Pb$_y$Sn$_{1-y}$)$_2$P$_2$S$_6$ mixed crystals, which include tricritical points and where a temperature …
We study Mn substitution for Ti in BaTiO3 with and without compensating oxygen vacancies using density functional theory (DFT) in combination with dynamical mean field theory (DMFT). We find strong charge and spin fluctuations. Without compensating oxygen vacancies, the ground state is found to be a quantum superposition of two distinct atomic valences, 3d4 and 3d5. Introducing a compensating oxygen vacancy at a neighboring site reduces both charge and spin fluctuations due to the reduction of electron hopping from Mn to its ligands. As a consequence, valence fluctuations are reduced, and is c…
We parametrize the Stillinger-Weber potential for 156 two-dimensional atomic crystals. Parameters for the Stillinger-Weber potential are obtained from the valence force field model following the analytic approach (Nanotechnology 26, 315706 (2015)), in which the valence force constants are determined by the phonon spectrum. The Stillinger-Weber potential is an efficient nonlinear interaction, and is applicable for numerical simulations of nonlinear physical or mechanical processes. The supplemental resources for all simulations in the present work are available online in Ref. 1, including a for…
We report a comprehensive magneto-transport study on single crystalline p-type topological crystalline insulator (TCI) SnTe, across the cubic-to-rhombohedral (R3m) transition which occurs as a function of temperature. The electrical resistivity of a well-characterized SnTe crystal shows evidence for the cubic-to-rhombohedral structural transition at T$_s$ $\sim$64,K and a carrier density of $\sim$1.8$\times$10$^{20}$ at 77,K. As a function of applied magnetic field perpendicular to the (100) plane, SnTe exhibits a large unsaturated linear magnetoresistance (LMR) reaching a value of 42% at 5K a…
Dark blue single crystals of Al$_{1.75}^{3+}$ Ti$_{1.0}^{4+}$ Ti$_{0.25}^{3+}$O$_5$ were grown with a novel synthesis method based on the reaction of a Ti3+/Ti4+ containing langbeinite melt and Al$_2$O$_3$. The obtained needles crystallize in the pseudobrookite structure and undergo two reversible phase transitions from orthorhombic Cmcm to C2/m first and subsequently to C2 symmetry. Like the known aluminum titanate pseudobrookites, anistropic thermal expansion is observed. The temperature evolution of the crystal structure reveals some insights into the mechanism leading to the decomposition …
The effect of quantum lattice fluctuations on the optical-absorption spectra in the ground state of halogen-bridged mixed-valence transition-metal linear-chain complexes is studied by using a one-dimensional extended Peierls-Hubbard model. The nonadiabatic effects due to finite phonon frequency $ω_π>0$ are treated through an energy-dependent electron-phonon scattering function $δ(k^{\prime},k)$ introduced by means of an unitary transformation. The calculated optical-absorption spectra do not have the inverse-square-root singularity, but they have a peak above the gap edge and there exists a si…
For $\rm Sn_2P_2S_6$ ferroelectrics by first-principles calculations an analysis of the $\rm P_2S_6$ cluster electronic structure and their comparison with crystal valence band in paraelectric and ferroelectric phases has been done and the origin of ferroelectricity has been outlined. It was established that the spontaneous polarization follows from the stereochemical activity of the electron lone pair of tin cations that is determined by hybridization with $\rm P_2S_6$ molecular orbitals. Increase of the chemical bonds covalence and their rearrangement are related to the valence band changes …
A single crystal monolith of La0.9Sr0.1FeO3 and thin pulsed laser deposited film of La0.8Sr0.2Fe0.8Ni0.2O3 were subject to angle integrated valence band photoemission spectroscopy in ultra high vacuum and conductivity experiments in ambient air at temperatures from 300 K to 800 K. Except for several sputtering and annealing cycles, the specimen were not prepared in-situ.. Peculiar changes in the temperature dependent, bulk representative conductivity profile as a result of reversible phase transitions, and irreversible chemical changes are semi-quantitatively reflected by the intensity variati…
An expression is derived within the framework of the Debye-Hückel approximation for the screening length of a field in a p-type semiconductor taking into account the energy spread of immobile acceptor levels and the density of states tail of the valence band. It is shown that the screening length depends additively on the product of the carrier density and their drift mobility to diffusion coefficient ratio (for free holes in valence band and holes hopping via acceptors).
The hexagonal ZrNiAl-type (space group: P-62m) and the tetragonal Mo2FeB2-type (space group: P4/mbm) structures, which are frequently formed in the same Yb-based alloys and exhibit physical properties related to valence-fluctuation, can be regarded as approximants of a hypothetical dodecagonal quasicrystal. Using Pd-Sn-Yb system as an example, a model of quasicrystal structure has been constructed, of which 5-dimensional crystal (space group: P12/mmm, aDD=5.66 Å and c=3.72 Å) consists of four types of acceptance regions located at the following crystallographic sites; Yb [00000], Pd[1/3 0 1/3 …
Materials with strong magnetoresistive responses are the backbone of spintronic technology, magnetic sensors, and hard drives. Among them, manganese oxides with a mixed valence and a cubic perovskite structure stand out due to their colossal magnetoresistance (CMR). A double exchange interaction underlies the CMR in manganates, whereby charge transport is enhanced when the spins on neighboring Mn3+ and Mn4+ ions are parallel. Prior efforts to find different materials or mechanisms for CMR resulted in a much smaller effect. Here we show an enormous CMR at low temperatures in EuCd2P2 without man…
We have calculated the conduction-to-conduction and valence-to-valence absorption spectrum of bound states in (In,Ga)As/GaAs quantum dots charged with up to three electrons or holes. Several features emerge: (i) In pure (non-alloyed) InAs/GaAs dots, the 1S-1P_1 and 1S-1P_2 conduction intraband transitions are fully in-plane polarized along [1\bar 10] and [110], respectively, while valence transitions are weakly polarized because the hole P states do not show any in-plane preferential orientation. (ii) In alloyed In_{0.6}Ga_{0.4}As/GaAs dots the [110] and [1\bar 10] polarization of the correspo…
The origin of magnetic frustration was stated and the ions whose shift is accompanied by emerging magnetic ordering and ferroelectricity in TbMn2O5 and BiMn2O5 were determined on the basis of calculation of magnetic coupling parameters by using the structural data. The displacements accompanying the magnetic ordering are not polar, they just induce changes of bond valence (charge disordering) of Mn1 and Mn2, thus creating instability of the crystal structure. To approximate again the bond valence to the initial value (charge ordering) under magnetic ordering conditions is possible only due to …
Mixed-valence compound Pb3O4 (minium) has been studied using X-ray absorption near-edge structure (XANES) spectroscopy and DFT calculations. In spite of presence of two valence states of lead [Pb(II) and Pb(IV)], the XANES spectrum of studied system is corresponding to apparently unified, an intermediate valence state of Pb. On the other hand, the 207Pb NMR spectra definitely show two different spectral bands corresponding to different Pb2+ and Pb4+ ions in Pb3O4 crystal structure. The explanation of this contradiction is related to the basics of XANES and NMR spectroscopy.
Valence-band and conduction-band electronic structure of CrS (d=0) and Cr5S6 (d=0.17) has been investigated by means of photoemission and inverse-photoemission spectroscopies. Bandwidth of the valence bands of Cr5S6 (8.5 eV) is wider than that of CrS (8.1 eV), though the Cr 3d partial density of states evaluated from the Cr 3p-3d resonant photoemission spectroscopy is almost unchanged between the two compounds with respect to the shapes including binding energies. The Cr 3d (t2g) exchange splitting energies of CrS and Cr5S6 are determined to be 3.9 and 3.3 eV, respectively.
GeO$_2$ has an $α$-quartz-type crystal structure with a very wide fundamental band gap of 6.6 eV and is a good insulator. Here we find that the stable rutile-GeO$_2$ polymorph with a 4.6 eV band gap has a surprisingly low $\sim$6.8 eV ionization potential, as predicted from the band alignment using first-principles calculations. Because of the short O$-$O distances in the rutile structure containing cations of small effective ionic radii such as Ge$^{4+}$, the antibonding interaction between O 2p orbitals raises the valence band maximum energy level to an extent that hole doping appears feasib…
Unraveling atomic-resolution valence electron energy-loss spectroscopic imaging in a single-crystal CaNb2O6
Lehigh University（利哈伊大学）；National Taipei University of Technology（台北科技大学）；Scientific Consulting, Research & Technical Service（科学咨询、研究与技术服务）；Brookhaven National Laboratory（布鲁克海文国家实验室）；National Taipei University of Science and Technology（台北科技大学）
X-ray magnetic circular dichroism and resonant inelastic X-ray scattering explained: role of many-body correlation and valence fluctuations
Seoul National University（首尔大学）；Institute for Basic Science（基础科学研究院）；SLAC National Accelerator Laboratory（斯坦福直线加速器国家实验室）；Fudan University（复旦大学）；University of California, Davis（加州大学戴维斯分校）；University of Illinois（伊利诺伊大学）；National Institute of Standards and Technology（美国国家标准与技术研究院）
We present a study of the static magnetic properties and spin dynamics in Cobalt valence tautomers (VT), molecules where a low-spin (LS) to high-spin (HS) crossover driven by an intramolecular electron transfer can be controlled by the temperature, by the external pressure or by light irradiation. In the investigated complex, a LS-Co(III) ion bound to a dinegative organic ligand can be reversibly converted into the HS-Co(II) bound to a mononegative one. By combining magnetization measurements with Nuclear Magnetic Resonance (NMR) and Muon Spin Relaxation (μSR), we have investigated the static …
We report on the valence fluctuation of Ce in CeMo$_{2}$Si$_{2}$C as studied by means of magnetic susceptibility $χ(T)$, specific heat $C(T)$, electrical resistivity $ρ(T)$ and x-ray absorption spectroscopy. Powder x-ray diffraction revealed that CeMo$_{2}$Si$_{2}$C crystallizes in CeCr$_{2}$Si$_{2}$C-type layered tetragonal crystal structure (space group \textit{P4/mmm}). The unit cell volume of CeMo$_{2}$Si$_{2}$C deviates from the expected lanthanide contraction, indicating non-trivalent state of Ce ions in this compound. The observed weak temperature dependence of the magnetic susceptibili…
We study the valence band structure of ReSe$_{2}$ crystals with varying thickness down to a single layer using nanoscale angle-resolved photoemission spectroscopy and density functional theory. The width of the top valence band in the direction perpendicular to the rhenium chains decreases with decreasing number of layers, from 280 meV for the bulk to 61 meV for monolayer. This demonstrates increase of in-plane anisotropy induced by changes in the interlayer coupling and suggests progressively more one-dimensional character of electronic states in few-layer rhenium dichalcogenides.
Plastic deformation mediated by collective dislocation dynamics is investigated in the two-dimensional phase-field crystal model of sheared single crystals. We find that intermittent fluctuations in the dislocation population number accompany bursts in the plastic strain-rate fluctuations. Dislocation number fluctuations exhibit a power-law spectral density $1/f^2$ at high frequencies $f$. The probability distribution of number fluctuations becomes bimodal at low driving rates corresponding to a scenario where low density of defects alternate at irregular times with high population of defects.…
Using density functional methods we calculated structural and electronic properties of bulk chloroform and bromoform intercalated C60, C60 2CHX3 (X=Cl,Br). Both compounds are narrow band insulator materials with a gap between valence and conduction bands larger than 1 eV. The calculated widths of the valence and conduction bands are 0.4-0.6 eV and 0.3-0.4 eV, respectively. The orbitals of the haloform molecules overlap with the $π$ orbitals of the fullerene molecules and the p-type orbitals of halogen atoms significantly contribute to the valence and conduction bands of C60 2CHX3. Charging wit…
A novel property of the quantum critical heavy fermion superconductor $β$-YbAlB$_4$ is revealed theoretically. By analyzing the crystalline electronic field (CEF) on the basis of the hybridization picture, odd parity CEF is shown to exist because of sevenfold configuration of B atoms around Yb, which breaks the local inversion symmetry. This allows onsite admixture of 4f and 5d wavefunctions with a pure imaginary coefficient, giving rise to the magnetic toroidal (MT) degree of freedom. By constructing a realistic minimal model for $β$-YbAlB$_4$, we show that onsite 4f-5d Coulomb repulsion driv…
