SEARCH · Search NASA
Results for “CRYSTAL FIELD”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Oxidation and crystal field effects in uranium
An in-depth exploration of oxidation in uranium has been pursued. This includes the utilization of soft x-ray absorption spectroscopy, hard x-ray absorption near-edge structure, resonant (hard) x-ray emission spectroscopy, cluster calculations, and a branching ratio analysis founded on atomic theory. The samples utilized were uranium dioxide (UO 2 ), uranium trioxide (UO 3 ), and uranium tetrafluoride (UF 4 ). A report on the role of nonspherical perturbations, i.e., crystal or ligand field effects, will be presented.
Inductive crystal field control in layered metal oxides with correlated electrons
Not Available
Coupling between phonon and crystal-field excitations in multiferroic PrFe 3 ( BO 3 ) 4
Far-infrared reflection and ellipsometry measurements on multiferroic PrFe 3 ( BO 3 ) 4 and SmFe 3 ( BO 3 ) 4 single crystals were used to investigate the interaction between lattice phonons and electronic excitations associated with 4 f crystal-field transitions. A temperature-dependent interference between two types of excitations was observed in PrFe 3 ( BO 3 ) 4 in which the frequency of 4 f crystal-field electronic excitation of Pr 3 + falls into the TO-LO frequency interval of the optical phonon mode near 50 cm - 1 (1.5 THz). Experimental data were explained on the basis of a theoretical model of coupled electron-phonon modes. The fitting procedure revealed the value 14.8 cm - 1 for the electron-phonon coupling constant. This rather large value points to an essential role played by the electron-phonon interaction in the physics of multiferroics.
Exchange field effect in the crystal-field ground state of Ce M Al 4 Si 2
The crystal-field ground-state wave functions of the tetragonal, magnetically ordering Kondo lattice materials CeMAl 4 Si 2 (M = Rh, Ir, and Pt) are determined in this paper with low-temperature linearly polarized soft-x-ray absorption spectroscopy, and estimates for the crystal-field splittings are given from the temperature evolution of the linear dichroism. Values for the dominant exchange field in the magnetically ordered phases can be obtained from fitting the influence of magnetic order on the linear dichroism. The direction of the required exchange field is || c for the antiferromagnetic Rh and Ir compounds, with the corresponding strength of the order of λ ex ≈ 6 meV (65 K). Finally and furthermore, the presence of Kondo screening in the Rh and Ir compound is demonstrated on the basis of the absorption due to f 0 in the initial state.
Quenched crystal-field disorder and magnetic liquid ground states in Tb 2 Sn 2 - x Ti x O 7 [Crystal field disorder in the quantum spin ice ground state of Tb2Sn2-xTixO7]
Solid-solutions of the "soft" quantum spin ice pyrochlore magnets Tb 2 B 2 O 7 with B=Ti and Sn display a novel magnetic ground state in the presence of strong B-site disorder, characterized by a low susceptibility and strong spin fluctuations to temperatures below 0.1 K. These materials have been studied using ac-susceptibility and muSR techniques to very low temperatures, and time-of-flight inelastic neutron scattering techniques to 1.5 K. Remarkably, neutron spectroscopy of the Tb 3+ crystal field levels appropriate to at high B-site mixing (0.5 < x < 1.5 in Tb 2 Sn 2-x Ti x O 7 ) reveal that the doublet ground and first excited states present as continua in energy, while transitions to singlet excited states at higher energies simply interpolate between those of the end members of the solid solution. The resulting ground state suggests an extreme version of a random-anisotropy magnet, with many local moments and anisotropies, depending on the precise local configuration of the six B sites neighboring each magnetic Tb 3+ ion.
Loss for photoemission versus gain for Auger: Direct experimental evidence of crystal-field splitting and charge transfer in photoelectron spectroscopy
Here, we find a 5 eV satellite in the Ti1s photoelectron spectrum of the transition-metal oxide SrTiO 3 . This satellite appears in addition to the well-studied 13 eV structure that is typically associated with the Ti2p core line. We give direct experimental evidence that the presence of two satellites is due to the crystal-field splitting of the metal 3d orbitals. They originate from ligand 2pt 2 g → metal3dt 2 g and ligand 2pe g → metal 3de g monopole charge-transfer excitations within the sudden approximation of quantum mechanics. This assignment is made by the energetics of the resonant and high-energy threshold behaviors of the TiK–L 2 L 3 Auger decay that follows Ti1s photoionization.
Atomic density functional and diagram of structures in the phase field crystal model
The phase field crystal model provides a continual description of the atomic density over the diffusion time of reactions. We consider a homogeneous structure (liquid) and a perfect periodic crystal, which are constructed from the one-mode approximation of the phase field crystal model. A diagram of 2D structures is constructed from the analytic solutions of the model using atomic density functionals. The diagram predicts equilibrium atomic configurations for transitions from the metastable state and includes the domains of existence of homogeneous, triangular, and striped structures corresponding to a liquid, a body-centered cubic crystal, and a longitudinal cross section of cylindrical tubes. The method developed here is employed for constructing the diagram for the homogeneous liquid phase and the body-centered iron lattice. The expression for the free energy is derived analytically from density functional theory. The specific features of approximating the phase field crystal model are compared with the approximations and conclusions of the weak crystallization and 2D melting theories.
Simultaneously optimizing fluorescent and paramagnetic properties of bifunctional NaGdF{sub 4}:Yb{sup 3+}/Er{sup 3+} nanocrystals by crystal field tuning
Graphical abstract: Crystal field tuning is a powerful approach for simultaneously enhancing the optical and magnetic properties of lanthanide-doped NaGdF{sub 4} bi-functional nanocrystals. - Abstract: Here, we show the simultaneous enhancement of fluorescent and paramagnetic properties in bifunctional NaGdF{sub 4}:Yb{sup 3+}/Er{sup 3+} nanocrystals by crystal field tuning. The energy level splitting calculation indicates, that lanthanide ionic pairs La{sup 3+}/Lu{sup 3+} introduced into the NaGdF{sub 4} host can modify the crystal field around emitters (e.g., Er{sup 3+} and Tm{sup 3+}) and sensitizers (e.g., Yb{sup 3+}) that result in the broadening of crystal field splitting of energy levels and the abundant multi-site distribution of upconversion luminescence. The optimization of the paramagnetic properties in NaGdF{sub 4} doped with emitters and sensitizers is ascribed to the lowering of anti-ferromagnetic coupling.
Crystal field parameters and energy levels scheme of trivalent chromium doped BSO
The aim of this paper is to give an analysis of crystal field parameters and energy levels schemes for the above doped material, in order to give a reliable explanation for experimental data. The crystal field parameters have been modeled in the frame of Exchange Charge Model (ECM) of the crystal field theory, taken into account the geometry of systems, with actually site symmetry of the impurity ions. The effect of the charges of the ligands and covalence bonding between chromium cation and oxygen anions, in the cluster approach, also were taken into account. With the obtained values of the crystal field parameters we simulated the scheme of energy levels of chromium ions by diagonalizing the matrix of the Hamiltonian of the doped crystal. The obtained energy levels and estimated Racah parameters B and C were compared with the experimental spectroscopic data and discussed. Comparison with experiment shows that the results are quite satisfactory which justify the model and simulation scheme used for the title system.
Unconventional crystal-field splitting in noncentrosymmetric BaTiO 3 thin films
Understanding the crystal-field splitting and orbital polarization in noncentrosymmetric systems such as ferroelectric materials is fundamentally important. In this work, taking BaTiO 3 as a representative material, we investigate titanium crystal-field splitting and orbital polarization in noncentrosymmetric TiO 6 octahedra with resonant x-ray linear dichroism at the Ti L 2,3 edge. The high-quality BaTiO 3 thin films were deposited on DyScO 3 (110) single crystal substrates in a layer-by-layer way by pulsed laser deposition. The reflection high-energy electron diffraction and element specific x-ray absorption spectroscopy were performed to characterize the structural and electronic properties of the films. In sharp contrast to conventional crystal-field splitting and orbital configuration (d xz /d yz < d xy < d 3z 2 -r 2 < d x 2 -y 2 or d xy < d xz /d yz < d x 2 -y 2 < d 3z 2 -r 2 ) expected from compressive or tensile epitaxial strain, respectively, it is revealed that d xz , d yz , and d xy orbitals are nearly degenerate, whereas d 3z 2 -r 2 and d x 2 -y 2 orbitals are split with an energy gap ~100 meV in the epitaxial BaTiO 3 films. We find that the unexpected degenerate orbitals d xz /d yz /d xy result from the competition between the orbital splitting induced by epitaxial strain and that induced by polar distortions of BaTiO 3 films. Our results provide a route to manipulate orbital degree of freedom by switching electric polarization in ferroelectric materials.
Random Crystal Field Effect on the Kinetic Spin-1 and Spin-3/2 Under a Time-Dependent Oscillating Field Phase Transitions
The effect of random crystal field on the stationary states of the kinetic spin-1 and spin-3/2 Blume-Capel model is investigated within the framework of the mean field approach. The Glauber-type stochastic dynamics is used to describe the time evolution of the system which is subjected to a time-dependent oscillating external magnetic field. The model exhibits first- and second-order transitions as well as dynamical tricritical, triple and an isolated critical end points. We found that the system displays reentrant phenomenon for both α = 0 and α > 0. Moreover, the system exhibits in the phase space a fixed points and limit cycles with circle, elliptic and parallelogram shapes.
Hybrid excitations due to crystal field, spin-orbit coupling, and spin waves in LiFePO 4
Here, we report on the spin waves and crystal field excitations in single crystal LiFePO 4 by inelastic neutron scattering over a wide range of temperatures, below and above the antiferromagnetic transition of this system. In particular, we find extra excitations below T N = 50 K that are nearly dispersionless and are most intense around magnetic zone centers. Furthermore, we show that these excitations correspond to transitions between thermally occupied excited states of Fe 2 + due to splitting of the S = 2 levels that arise from the crystal field and spin-orbit interactions. These excitations are further amplified by the highly distorted nature of the oxygen octahedron surrounding the iron atoms. Above T N , magnetic fluctuations are observed up to at least 720 K, with an additional inelastic excitation around 4 meV, which we attribute to single-ion effects, as its intensity weakens slightly at 720 K compared to 100 K, which is consistent with the calculated cross sections using a single-ion model. This theoretical analysis, using the MF-RPA model, provides both detailed spectra of the Fe d shell and estimates of the average ordered magnetic moment and T N . By applying the MF-RPA model to a number of existing spin-wave results from other Li M PO 4 ( M = Mn , Co, and Ni), we are able to obtain reasonable predictions for the moment sizes and transition temperatures.
Linearly first- and second-order, unconditionally energy stable schemes for the phase field crystal model
In this paper, we develop a series of linear, unconditionally energy stable numerical schemes for solving the classical phase field crystal model. The temporal discretizations are based on the first order Euler method, the second order backward differentiation formulas (BDF2) and the second order Crank–Nicolson method, respectively. The schemes lead to linear elliptic equations to be solved at each time step, and the induced linear systems are symmetric positive definite. We prove that all three schemes are unconditionally energy stable rigorously. Various classical numerical experiments in 2D and 3D are performed to validate the accuracy and efficiency of the proposed schemes.
Crystal fields of porphyrins and phthalocyanines from polarization-dependent 2p-to-3d multiplets
Polarization-dependent X-ray absorption spectroscopy is combined with density functional calculations and atomic multiplet calculations to determine the crystal field parameters 10Dq, Ds, and Dt of transition metal phthalocyanines and octaethylporphyrins (Mn, Fe, Co, Ni). The polarization dependence facilitates the assignment of the multiplets in terms of in-plane and out-of-plane orbitals and avoids ambiguities. Crystal field values from density functional calculations provide starting values close to the optimum fit of the data. The resulting systematics of the crystal field can be used for optimizing electron-hole separation in dye-sensitized solar cells.
Neutron spectroscopic study of crystal field excitations in Tb 2 Ti 2 O 7 and Tb 2 Sn 2 O 7
We present time-of-flight inelastic neutron scattering measurements at low temperature on powder samples of the magnetic pyrochlore oxides Tb 2 Ti 2 O 7 and Tb 2 Sn 2 O 7 . These two materials possess related, but different ground states, with Tb 2 Sn 2 O 7 displaying "soft" spin ice order below T N approx 0.87 K, while Tb 2 Ti 2 O 7 enters a hybrid, glassy-spin ice state below T g approx 0.2 K. Our neutron measurements, performed at T = 1.5 K and 30 K, probe the crystal field states associated with the J = 6 states of Tb 3+ within the appropriate Fd3-barm pyrochlore environment. These crystal field states determine the size and anisotropy of the Tb 3+ magnetic moment in each material's ground state, information that is an essential starting point for any description of the low temperature phase behavior and spin dynamics in Tb 2 Ti 2 O 7 and Tb 2 Sn 2 O 7 . While these two materials have much in common, the cubic stanate lattice is expanded compared to the cubic titanate lattice. As our measurements show, this translates into a factor of approx 2 increase in the crystal field bandwidth of the 2J +1 = 13 states in Tb 2 Ti 2 O 7 compared with Tb 2 Sn 2 O 7 . Our results are consistent with previous measurements on crystal field states in Tb 2 Sn 2 O 7 , wherein the ground state doublet corresponds primarily to mJ = {vert_bar}+-5> and the first excited state doublet to mJ = {vert_bar}+-4>. In contrast, our results on Tb 2 Ti 2 O 7 differ markedly from earlier studies, showing that the ground state doublet corresponds to a significant mixture of mJ = {vert_bar}+-5>, mJ = {vert_bar}+-4> and mJ = {vert_bar}+-2>, while the first excited state doublet corresponds to a mixture of mJ = {vert_bar}+-4>, mJ = {vert_bar}+-5> and mJ = {vert_bar}+-1>. We discuss these results in the context of proposed mechanisms for the failure of Tb 2 Ti 2 O 7 to develop conventional long range order down to 50 mK.
The roles of 4f- and 5f-orbitals in bonding: A magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study
The electronic structures of 4f 3 /5f 3 Cp" 3 M and Cp" 3 M·alkylisocyanide complexes, where Cp" is 1,3-bis-(trimethylsilyl)cyclopentadienyl, are explored with a focus on the splitting of the f-orbitals, which provides information about the strengths of the metal–ligand interactions. While the f-orbital splitting in many lanthanide complexes has been reported in detail, experimental determination of the f-orbital splitting in actinide complexes remains rare in systems other than halide and oxide compounds, since the experimental approach, crystal field analysis, is generally significantly more difficult for actinide complexes than for lanthanide complexes. In this study, a set of analogous neodymium(III) and uranium(III) tris-cyclopentadienyl complexes and their isocyanide adducts was characterized by electron paramagnetic resonance (EPR) spectroscopy and magnetic susceptibility. The crystal field model was parameterized by combined fitting of EPR and susceptibility data, yielding an accurate description of f-orbital splitting. The isocyanide derivatives were also studied using density functional theory, resulting in f-orbital splitting that is consistent with crystal field fitting, and by multi-reference wavefunction calculations that support the electronic structure analysis derived from the crystal-field calculations. The results highlight that the 5f-orbitals, but not the 4f-orbitals, are significantly involved in bonding to the isocyanide ligands. The main interaction between isocyanide ligand and the metal center is a σ-bond, with additional 5f to π* donation for the uranium complexes. As a result, while interaction with the isocyanide π*-orbitals lowers the energies of the 5f xz 2 and 5f yz 2- orbitals, spin–orbit coupling greatly reduces the population of 5f xz 2 and 5f yz 2 in the ground state.