Coherent electronic coupling versus localization in individual molecular dimers

We have investigated electronic excitation transfer in individual molecular dimers by time and spectrally resolved confocal fluorescence microscopy. The single molecule measurements allow for directly probing the distribution of the electronic coupling strengths due to static disorder in the polymer host. We find dimers where the excitation is delocalized (superradiant emission) while for others emission originates from a localized state. Transitions between delocalized and localized states as observed for a given dimer are attributed to structural fluctuations of the guest-host system.     

Magnetic circular dichroism from the impurity band in III-V diluted magnetic semiconductors

The magnetic circular dichroism of III-V diluted magnetic semiconductors, calculated within a theoretical framework suitable for highly disordered materials, is shown to be dominated by optical transitions between the bulk bands and an impurity band formed from magnetic dopant states. The real-space Green's functions incorporate spatial correlations in the disordered conduction band and valence-band electronic structure, and include extended and localized states on an equal basis. Our findings reconcile unusual trends in the experimental magnetic circular dichroism in III-V diluted magnetic semiconductors with the antiferromagnetic p-d exchange interaction between a magnetic dopant spin and its host.     

Ultrafast electron dynamics in amorphous and crystalline D2O layers on Ru(0 0 1)

Femtosecond dynamics of excess electrons photo-injected into amorphous and crystalline D₂O layers on Ru(0 0 1) have been investigated by time-resolved two-photon photoelectron spectroscopy. In the crystalline case, excited electrons are transferred into delocalized states considered as image potential states in the conduction band of ice and relax back to the metal on an ultrafast time scale. The life time of the n = 1 image potential state is <5 fs. In the amorphous case, spectral features arise from delocalized and localized electronic states. Relaxation of delocalized electrons back to the metal is as fast as in the crystalline case. The binding energy of localized electrons, however, is found to increase as a function of time delay by 1 eV/ps, which is attributed to the formation of solvated electrons. Such energetic stabilization starting at the bottom of the conduction band is clearly absent in crystalline layers. This pronounced correlation of electronic structure and electron dynamics with molecular structure is associated with the presence of localized states near the bottom of the conduction band in amorphous ice. Such localized states are absent for perfect periodic crystalline structures but prevail in amorphous systems where they serve as precursor sites for electron solvation.     

Spin-polarized ground state for interacting electrons in two dimensions

We study numerically the ground state magnetization for clusters of interacting electrons in two dimensions in the regime where the single particle wave functions are localized by disorder. It is found that the Coulomb interaction leads to a spontaneous ground state magnetization. For a constant electronic density, the total spin increases linearly with the number of particles, suggesting a ferromagnetic ground state in the thermodynamic limit. The magnetization is suppressed when the single particle states become delocalized.     

LSDA+U方法对富勒烯内掺稀土原子的结构和电子结构的理论研究

在密度泛函理论框架下的局域密度近似方法 (LDA)能够准确地给出广延态电子体系的基态电子结构 ,是研究复杂体系的电子结构的一种非常成功的方法。由于这种方法不含参数 ,被广泛地用于微观体系的研究。但是 ,在处理的体系中含有局域电子时 ,由于方法的局限 ,给出的结果与光电子谱等试验结果符合得并不好。LSDA U方法是在局域自旋密度近似的框架下 ,结合模型哈密顿方法 ,对局域电子采用哈伯德模型描述 ,用以改进局域密度近似计算的一种方法。本文利用局域密度近似下的离散变分团簇方法 (DVM )对于内嵌稀土原子的富勒烯Er2 @C82 、Tm @C82 的电子结构进行了第一性原理的计算。对于体系中所含的稀土原子存在强关联的 4f电子 ,在LDA方法计算的基础上 ,考虑 4f电子在位库仑作用 ,用LSDA U方法研究了上述体系 ,得到了可以和XPS和吸收谱相比较的结果。     

镓掺杂氧化锌和硫化锌电子结构差异的第一性原理

运用第一性原理进行了相关计算研究Ga掺杂的ZnO和ZnS的电子结构的差异. 结果表明,LDA和LDA+U计算的结果在定性上是一致的. 掺杂Ga以后,ZnO和ZnS的费米能级处均出现杂质态. 掺杂中的ZnO,杂质态在导带是离域的. 掺杂后的ZnS,虽然p态比较离域,但其s态在费米能级处却是局域的. 前线轨道的电荷密度分布也给出了相同的信息. 交换ZnO和ZnS的晶格结构,结果不变. 局域化的Ga-s态是导致掺杂ZnS电学性能差的原因.     

Charged excitons in quantum dots: novel magnetic behavior and Auger processes

We describe theoretically multiply-charged excitons interacting with a continuum of delocalized states. Such excitons exist in relatively shallow quantum dots and have been observed in recent optical experiments on InAs self-assembled dots. The interaction of an exciton and delocalized states occurs via Auger-like processes. To describe the optical spectra, we employ the Anderson-like Hamiltonian by including the interaction between the localized exciton and delocalized states of the wetting layer. In the absence of a magnetic field, the photoluminescence line shapes exhibit interference effects. When a magnetic field is applied, the photoluminescence spectrum demonstrates anticrossings with the Landau levels of the extended states. We show that the magnetic-field behavior of charged excitons is very different to that of diamagnetic excitons in three and two-dimensional systems.     

The role of defect states in the creation of photoluminescence in SrTiO<Subscript>3</Subscript>

We discuss the nature of visible photoluminescence at room temperature in amorphous strontium titanate in the light of the results of a recent experimental and quantum mechanical theoretical study. Our calculation of the electronic structure involves the use of first-principles molecular calculations to simulate the variation of the electronic structure in the strontium titanate crystalline phase, which is known to have a direct band gap, and we also make an in-depth examination of amorphous strontium titanate. The results of our simulations of amorphous strontium titanate indicate that the formation of five-fold coordination in the amorphous system may introduce delocalized electronic levels in the highest occupied molecular orbital and the lowest unoccupied molecular orbital. These delocalized electronic levels are ascribed to the formation of a tail in the absorbance-spectrum curve. Optical absorption measurements experimentally showed the presence of a tail. The results are interpreted by the nature of these exponential optical edges and tails associated with defects promoted by the disordered structure of the amorphous material. We associate them with localized states in the band gap. Received: 15 January 2002 / Accepted: 7 August 2002 / Published online: 4 December 2002 RID="*" ID="*"Corresponding author. Fax: +55-16/2615-215, E-mail: derl@power.ufscar.br     

Unraveling the solid-liquid-vapor phase transition dynamics at the atomic level with ultrafast x-ray absorption near-edge spectroscopy

X-ray absorption near-edge spectroscopy (XANES) is a powerful probe of electronic and atomic structures in various media, ranging from molecules to condensed matter. We show how ultrafast time resolution opens new possibilities to investigate highly nonequilibrium states of matter including phase transitions. Based on a tabletop laser-plasma ultrafast x-ray source, we have performed a time-resolved (～3 ps) XANES experiment that reveals the evolution of an aluminum foil at the atomic level, when undergoing ultrafast laser heating and ablation. X-ray absorption spectra highlight an ultrafast transition from the crystalline solid to the disordered liquid followed by a progressive transition of the delocalized valence electronic structure (metal) down to localized atomic orbitals (nonmetal-vapor), as the average distance between atoms increases.     

Electronic structure of ErS and PrS: Analysis of the sulfur K-edge XANES spectra

K-edge XANES spectra of sulfur in ErS and PrS have been measured. A detailed analysis of the electronic structure of ErS and PrS was carried out by the full-scale multiple scattering method, and a good agreement with experimental spectra was obtained. The fine structure of unoccupied sulfur states in the conduction band was determined. The unoccupied d states of praseodymium in PrS are shown to interact with the sulfur p states to expel the sulfur delocalized states from the energy region where the states of the rare-earth elements are localized.     

Anderson localization in a two-dimensional random gap model

We study the properties of the spinor wavefunction in a strongly disordered environment on a two-dimensional lattice. By employing a transfer-matrix calculation we find that there is a transition from delocalized to localized states at a critical value of the disorder strength. We prove that there exists an Anderson localized phase with exponentially decaying correlations for sufficiently strong scattering. Our results indicate that suppressed backscattering is not sufficient to prevent Anderson localization of surface states in topological insulators.     

Charge qubit rotations in a double-dot nanostructure

Quantum operations with a charge solid-state qubit whose logical states are formed by two spatially separated localized states of an electron in the double-dot structure are studied theoretically. We show that it is possible to perform various one-qubit rotations making use of the microwave pulses tuned to the resonances between the localized states and the excited state delocalized over the nanostructure. An explicit analytic expression for the time-dependent electron state vector is derived, and the appropriate pulse parameters are determined.     

Superinsulator as a phase of bi-particle localized states

We propose a physical picture of superinsulator observed recently in experiments with superconducting films in a magnetic field. On the basis of previous numerical studies we argue that a moderate attraction creates bi-particle localized states at intermediate disorder strength when noninteracting electron states are delocalized and metallic. Our present numerical study show that such localized pairs are broken by a static electric field which strength is above a certain threshold. We argue that such a breaking of localized pairs by a static field is at the origin of superinsulator breaking with a current jump observed experimentally above a certain critical voltage.     

Enhanced infrared transmission through subwavelength coaxial metallic arrays

We report the observation of enhanced near-infrared transmission through arrays of subwavelength coaxial metallic structures compared with that through comparable diameter hole arrays as a result of localized electromagnetic modes supported by the complex coaxial unit cell. Polarization and angle-dependent transmission measurements clearly demonstrate the coupling between this localized mode and delocalized surface plasmon modes. A generalized, multiple discrete states Fano line shape provides a good fit to the experimental results.     

Horizontal rolls in convective flow above a partially heated surface

Considering the nonlinearity arising from the interaction between electrons and lattice vibrations, an effective electronic model with a self-interaction cubic term is employed to study the interplay between electron-electron and electron-phonon interactions. Based on numerical solutions of the time-dependent nonlinear Schroedinger equation for an initially localized two-electron singlet state, we show that the magnitude of the electron-phonon coupling χ necessary to promote the self-trapping of the electronic wave packet decreases as a function of the electron-electron interaction U. We show that such dependence is directly linked to the narrowing of the band of bounded two-electron states as U increases. We obtain the transition line in the χ × U parameter space separating the phases of self-trapped and delocalized electronic wave packets. The present results indicates that nonlinear contributions plays a relevant role in the electronic wave packet dynamics, particularly in the regime of strongly correlated electrons.     

EPR spectra of the double triangular polyoxovanadates with exchange and electron transfer effects: Symmetry breaking and effective motional averaging

The interplay of isotropic exchange, antisymmetric (AS) exchange, and electron delocalization has been theoretically investigated for a system comprising two triangles, one with three localized d¹ spins, which gives rise to spin frustration effects, and the other with one d¹ center delocalized on the three sites. In the localized limit the AS exchange is partially reduced by the low symmetry components of an isotropic exchange (inter-triangle interaction) and splits the spin triplets only in the second order, contrary to what is found for a single triangular system where splitting of the spin doublet levels occurs in the first order. Zero-field splitting parameters depend on both AS exchange parameters and low symmetry components of the isotropic exchange. The EPR spectrum consists of intratriplet (Heisenberg type) and intertriplet (non-Heisenberg type) lines. AS exchange also induces singlet-triplet transitions. The EPR spectra of powder samples are generated for a domain of key parameters. Two different situations occur depending on the symmetry of the electronic states when the electron delocalization is taken into account. The orbital doublets of the localized system indicate a complete averaging of the exchange interactions, which results in effective enhancement of AS exchange. Unlike triplets, the orbital singlets are unaffected by a transfer process, developing only second-order AS exchange. Coexistence of localized and delocalized states is expected to be an intrinsic feature of exchange systems with partial delocalization. The relevance of these effects to the magnetic properties of exchange clusters is briefly discussed.     

Self-trapping of interacting electrons in crystalline nonlinear chains

Considering the nonlinearity arising from the interaction between electrons and latticevibrations, an effective electronic model with a self-interaction cubic term is employedto study the interplay between electron-electron and electron-phonon interactions. Basedon numerical solutions of the time-dependent nonlinear Schroedinger equation for aninitially localized two-electron singlet state, we show that the magnitude of theelectron-phonon coupling χ necessary to promote the self-trapping of theelectronic wave packet decreases as a function of the electron-electron interactionU. We show that such dependence is directly linked to the narrowing ofthe band of bounded two-electron states as U increases. We obtain thetransition line in the χ × U parameter space separatingthe phases of self-trapped and delocalized electronic wave packets. The present resultsindicates that nonlinear contributions plays a relevant role in the electronic wave packetdynamics, particularly in the regime of strongly correlated electrons.     

Novel Jeff=1/2 Mott state induced by relativistic spin-orbit coupling in Sr2IrO4

We investigated the electronic structure of 5d transition-metal oxide Sr2IrO4 using angle-resolved photoemission, optical conductivity, x-ray absorption measurements, and first-principles band calculations. The system was found to be well described by novel effective total angular momentum Jeff states, in which the relativistic spin-orbit coupling is fully taken into account under a large crystal field. Despite delocalized Ir 5d states, the Jeff states form such narrow bands that even a small correlation energy leads to the Jeff=1/2 Mott ground state with unique electronic and magnetic behaviors, suggesting a new class of Jeff quantum spin driven correlated-electron phenomena.     

Elusive <Emphasis Type="Italic">s-f</Emphasis> intrasite interactions and double exchange in solids: Ferromagnetic versus nonmagnetic ground state

From the theory of many-electron states in atoms, we know that there exists a strong Coulomb repulsion, which results in the electronic term structure of atoms and is responsible for Hund’s rules. By expanding the Coulomb on-site repulsion into a multipolar series, we derive this interaction and show that it is also present in solids as a correlation effect, which means that the interaction requires a multideterminant version of the Hartree-Fock method. Of particular interest is the case where this interaction couples states of localized (f) and delocalized (s) electrons. We show that the interaction is bilinear in the creation/annihilation operators for localized electrons and bilinear in the operators for conduction electrons. To study the coupling, we consider a simple model in the framework of an effective limited configuration interaction method with one localized f-electron and one itinerant s-electron per crystal site. The on-site multipole interaction between the f- and s-electrons is explicitly taken into account. It is shown that depending on the low-lying excitation spectrum imposed by the crystal electric field, the model can lead not only to ferromagnetism but also to a nonmagnetic state. The model is relevant for solids with localized and itinerant electron states.     

Electronic structure of Pu monochalcogenides and monopnictides

The electronic and magnetic properties of Pu monopnictides and monochalcogenides, PuX (X = N, P, As, Sb, Bi, O, S, Se, Te, Po), are studied using the self-interaction-corrected local spin-density approximation. This approach allows for an integer number of f-states to be localized, while the remaining f-electron degrees of freedom are available for band formation. By varying the relative proportions of localized and delocalized f-states, the energetically most favourable (groundstate) configuration can be established. We show that the experimental data can be interpreted in terms of the coexistence of both localized and delocalized f-states. Received 10 August 2001