Quantum chemical modelling of “green” luminescence in ABO perovskites

The origin of the intrinsic excitonic (“green”) luminescence in ABO₃ perovskites remains a hot topic over the last quarter of a century. We suggest as a theoretical interpretation for the “green” luminescence in these crystals, the recombination of electron and hole polarons forming a charge transfer vibronic exciton. In order to check quantitatively the proposed model, we performed quantum chemical calculations using the Intermediate Neglect of Differential Overlap (INDO) method combined with the periodic defect model. The luminescence energies calculated for four perovskite crystals are found to be in good agreement with experimental data. Received 19 December 2001 and Received in final form 14 March 2002 Published online 25 June 2002     

CEF nature of the magnetic excitations in ordered HoNi B C

The magnetic excitations in the antiferromagnetic phase of HoNi₂B₂C are studied by inelastic neutron scattering on single crystals for the first time. Spectra measured at constant T = 2 K along symmetry directions of the reciprocal space are well explained in terms of crystal electric field (CEF) magnetic excitons within the J = 8 ground state multiplet of Ho³⁺. Very modest bandwidth with planar energy dispersion describes the magnetic exciton dynamics. A perturbative model approach consisting of the CEF states in the effective exchange mean-field provides a simple but applicable characterization of the experimental observations. The microscopic determination of the relevant exchange parameters is discussed in connection with previous works on the subject. Received 25 February 2002 / Received in final form 13 May 2002 Published online 14 October 2002 RID="a" ID="a"e-mail: nordal.cavadini@psi.ch     

Ultrafast dynamics in the excited hydrogen atom transfer states of ammonia clusters

Neutral ammonia clusters (NH₃)_m are photo-excited to the electronic state by a deep UV femtosecond laser pump pulse. Within a few hundred femtoseconds a significant fraction of the clusters rearrange to form an H-transfer state (NH₃)_m-2NH₄(3s)NH₂ with the subunit NH₄ in its 3s electronic ground state. This state is then electronically excited by a time-delayed infrared control pulse of variable wavelength. Finally, a third (probe) pulse in the UV ionizes the clusters for detection. The lifetime of the excited (NH₃)_m-2NH₄(3p)NH₂ states is found to vary between 2.7 and 0.13 ps depending on cluster size and excitation energy. It increases drastically upon deuteration. The corresponding cluster size-dependent photoelectron spectra allow us to disentangle the underlying energetics of the excitation and ionization process and reveal additional processes, such as nonresonant ionization or dissociative ionization. The experimental findings suggest that the excited H-transfer ammonia complexes with m > 2 are deactivated by an internal conversion process back to the electronically lowest H-transfer state followed by fast dissociation. Received 22 September 2001 and Received in final form 31 January 2002     

The Al-Pd-Mn quasicrystalline approximant -phase revisited

A detailed investigation of the Fourier space of several Al-Pd-Mn samples with composition Al-72.6 at. %, Pd-22.9 at. %, Mn-4.5 at. % is reported. In the phase diagram of the Al-Pd-Mn ternary alloy, this composition corresponds to the so-called ξ' phase which was described as an icosahedral quasicrystalline approximant. By re-examining the Fourier space by means of X-ray diffraction (powder patterns and single crystal precession patterns), complex structures in close relation with the ξ'-phase have been observed. These long-range order complex structures are described as resulting from a periodic perturbation of the ξ' structure along the c direction. Two states with periodicities c (3 + τ) and c (5 + τ) have been observed in this study (τ: golden mean). Structural models based on periodic arrangements of “defects” layers separating layers of phase are proposed. These two states are certainly intermediate states between the phase and the metastable decagonal quasicrystalline phase. Received 11 April 2002 / Received in final form 24 June 2002 Published online 17 September 2002     

Oxygen K-edge in vanadium oxides: simulations and experiments

Band-structure (BS) calculations of the density of states (DOS) using the full potential augmented plane waves code WIEN97 were performed on the four single-valence vanadium oxides VO, V₂O₃, VO₂ and V₂O₅. The DOS are discussed with respect to the distortions of the VO₆ octahedra, the oxidation states of vanadium and the orbital hybridisations of oxygen atoms. The simulated oxygen K-edge fine structures (ELNES) calculated with the TELNES program were compared with experimental results obtained by electron energy-loss spectrometry (EELS), showing good agreement. We show that changes in the fine structures of the investigated vanadium oxides mainly result from changes in the O-p DOS and not from the shift of the DOS according to a rigid band model. Received 17 December 2001 / Received in final form 19 June 2002 Published online 13 August 2002     

Relation between vortex excitation and thermal conductivity in superconductors

Thermal conductivity κ _xx(T) under a field is investigated in d _{x2 - y2}-wave superconductors and isotropic s-wave superconductors by the linear response theory, using a microscopic wave function of the vortex lattice states. To study the origin of the different field dependence of κ_xx(T) between higher and lower temperature regions, we analyze the spatially-resolved thermal conductivity around a vortex at each temperature, which is related to the spectrum of the local density of states. We also discuss the electric conductivity in the same formulation for a comparison. Received 8 December 2001 and Received in final form 20 March 2002 Published online 6 June 2002     

Broad-band dielectric spectroscopy of Ba 2NaNb 5O 15 single crystal

Barium sodium niobate (BNN) single crystals are studied by IR spectroscopy, time-domain THz transmission spectroscopy, HF coaxial wave-guide technique and LF dielectric spectroscopy to cover the frequency range 10²-10¹⁴ Hz in a wide temperature interval. The dielectric response parallel and perpendicular to the polar c-axis is discussed. The ferroelectric transition at T _c = 830 K is driven by a relaxational soft mode coupled with another central-mode type relaxation which both gradually disappear on cooling in the ferroelectric phase. Below T _i the parameters of the expected IR active amplitudon were estimated. The low-temperature permittivity increase on cooling for the field direction has been explained by an incipient proper ferroelectric-ferroelastic transition driven by an IR and Raman active B₂-symmetry soft mode. Received 24 August 2002 Published online 19 December 2002 RID="a" ID="a"e-mail: buixader@fzu.cz     

Nonlinear dielectric response of antiferroelectric liquid crystals in the smectic Cα * phase

Nonlinear dielectric response of antiferroelectric liquid crystals has been studied in the smectic C_α* (SmC_α*) phase. The linear dielectric spectrum shows a single relaxation of Debye type and its relaxation frequency is as high as one hundred kHz. The profile of the third-order nonlinear dielectric spectrum varies in complex fashion with temperature. In the vicinity of the SmA-SmC_α* phase transition, experimentally obtained nonlinear spectra are well described by those calculated with phenomenological theory of Landau type. The soft mode of the SmC_α* phase shows critical slowing-down near the transition temperature. In the lower-temperature region of the SmC_α* phase, the contribution from the soft mode of the SmC_α* phase reduces and the other relaxation mode with Debye-type spectrum appears at several hundred Hz in the nonlinear spectrum. The appearance of this low-frequency mode suggests that the cooperative fluctuation of directors over long range exists in the SmC_α* phase. Received 19 April 2002 and Received in final form 23 July 2002 RID="a" ID="a"e-mail: kimura@exp.t.u-tokyo.ac.jp     

Maximally aligned states in 99Ag

Excited states of ⁹⁹Ag were populated via the ⁵⁰Cr + ⁵⁸Ni (261 MeV) reaction using the NORDBALL detector array equipped with charged-particle and neutron detector systems for reaction channel separation. On the basis of the measured γγ-coincidence relations and angular distribution ratios a significantly extended level scheme has been constructed up to E _x ∼ 7.8 MeV and I = 35/2. The experimental results were described within the framework of the shell model. Candidates for states fully aligned in the πg _9/2 ^-3ν(d _5/2, g _7/2)² valence configuration space were found at 4109 and 6265 keV. Received: 18 June 2002 / Accepted: 11 October 2002 / Published online: 4 February 2003 RID="a" ID="a"e-mail: sohler@atomki.hu Communicated by J. ?yst?     

Composite spin-triplet superconductivity in an symmetric lattice model

The two-channel Anderson lattice model which has SU (2) ⊗ SU (2) symmetry is of relevance to understanding of the magnetic, quadrupolar and superconducting phases in U_1-xTh_xBe₁₃ or Pr based skutterudite compounds such as PrFe₄P₁₂ or PrOs₄Sb₁₂. Possible unconventional superconducting phases of the model are explored. They are characterized by a composite order parameter comprising of a local magnetic or quadrupolar moment and a triplet conduction electron Cooper-pair. This binding of local degrees of freedom removes the entropy of the non Fermi-liquid normal state. We find superconducting transitions in the intermediate valence regime which are suppressed in the stable moment regime. The gap function is non analytic and odd in frequency: a pseudo-gap develops in the conduction electron density of states which vanishes as |ω| close to ω = 0. In the strong intermediate valent regime, the gap function acquires an additional -dependence. Received 28 February 2002 / Received in final form 18 April 2002 Published online 9 July 2002     

Third harmonic generation of laser radiation in Fe- and Zn-doped polyvinylpyrrolidone

The results of third-order nonlinear susceptibilities studies of Fe- and Zn-doped polyvinylpyrrolidone (PVP) aqueous solution in processes of third harmonic generation of Nd:YAG laser radiation are presented. Nonlinear susceptibilities of PVP:Fe and PVP:Zn were calculated to be 5×10^-13 esu and 3×10^-13 esu respectively. Third harmonic conversion efficiencies in these metallocomplexes were measured to be 8×10^-7 and 5×10^-7 respectively. The Z-scan method was applied to determine Kerr effect influence on frequency conversion process. The value of nonlinear refractive index of PVP:Fe at the wavelength of λ = 1064 nm was measured to be n ₂ = - 6.7×10^-13 esu. Received 30 November 2001 / Received in final form 27 March 2002 Published online 28 June 2002     

Nonlinear frequency conversion in 2D χ (2) photonic crystals and novel nonlinear double-circle construction

The analytic solution to the wave equation for small-signal sum-frequency process is derived in 2D χ ⁽²⁾ photonic crystals with use of the Green function method. It is predicted that the sum-frequency electrical field at quasi-phase matching (QPM) resonance is proportional to the angle-dependent effective crystal length. This implies that multiple wavelength QPM frequency conversion with controllable intensity output can be realized in a single 2D χ ⁽²⁾ photonic crystal. It is revealed that efficient frequency conversion requires both the QPM and the proper structure matching. A novel double-circle construction, different from the conventional Ewald construction, is presented to reflect important QPM processes. It is also shown that the QPM resonance tuning of second-harmonic generation can operate over the whole transparent wavelength range of crystals. Received 19 April 2001     

Magnetic relaxation in spinel Mo-ferrite and Ti substituted Mo-ferrite

A compensation temperature of 138 K was observed in the temperature-dependent magnetization curves of MoFe₂O₄. Relatively slow magnetization relaxation characterized the transitions between different spin states (compensated and uncompensated). Large magnetic after effect was found in time-dependent magnetization curves after heating or cooling from different characteristic temperatures for different spin states. The magnetic relaxation was nearly independent on magnetic field, supporting the presence of spin states and no involvement of domain structure. For the Ti substituted Mo_0.6Ti_0.4Fe₂O₄ sample, there were a compensation at ∼ 100 K and a maximum of magnetization at ∼ 175 K. Similar results of anomalous magnetic relaxation was observed in Ti substituted Mo-ferrite (Mo_0.6Ti_0.4Fe₂O₄). If the Mo_0.6Ti_0.4Fe₂O₄ sample was heated from 100 K to 235 K, the time-dependent magnetization curve could be considered as a combination of two magnetic relaxation processes. However, if the sample was heated from 100 K to 295 K, the time- dependent magnetization curve became complex. Received 30 October 2001 and Received in final form 21 January 2002     

Reactivity and magnetism of Fe/InAs(100) interfaces

Interface reaction and magnetism of epitaxially-grown Fe on InAs(100) are studied by core-level photoemission (As 3d and In 4d) and Fe 2p X-ray magnetic circular dichroism using synchrotron radiation. The reactivity of Fe/InAs(100) is relatively low compared to that of other interfaces involving deposition of 3d metals on III-V semiconductors. As a consequence, we observe a magnetic signal at Fe L_{2, 3} edges for the lowest thicknesses studied (1 ML). The atomic magnetic moment reaches a value close to that of the bulk α-Fe (2.2 μ _B) for Fe coverages exceeding 5 ML. A ferromagnetic compound with approximate stoichiometry of FeAs is formed at the interface. The orbital magnetism represents between 12 and 20% of the total momentum, due to 3d density of states depletion and to crystal-field modification of the electronic levels. These properties make the Fe/InAs(100) interface very promising for spin-tunneling devices. Received 4 April 2002 / Received in final form 13 May 2002 Published online 31 July 2002     

Electron-phonon interaction in carbon schwarzites

The recent synthesis of random schwarzites has stimulated the present ab initio calculation of the electronic structure and electron-phonon interaction in two different periodic D-type schwarzites, fcc-(C₂₈)₂ (made of 24 seven-membered rings per unit cell) and fcc-(C₆₄)₂ (made of 12 eight membered and 48 six-membered rings per unit cell). Like in fullerenes, also in schwarzites the electron-phonon interaction potential is found to increase with the absolute Gauss curvature, though it remains smaller than for doped fullerenes. Received 19 December 2002 Published online 1st April 2003 RID="a" ID="a"e-mail: marco.bernasconi@unimib.it     

Branched crystal morphology of linear polyethylene crystallized in a two-dimensional diffusion-controlled growth field

The branched crystal morphology of linear polyethylene formed at various temperatures from thin films has been studied by atomic-force microscopy (AFM), transmission electron microscopy (TEM), electron diffraction (ED) pattern and polymer decoration technique. Two types of branched patterns, i.e. dendrite and seaweed patterns, have been visualized. The fractal dimension d _f = 1.65 of both dendrite and some of seaweed patterns was obtained by using the box-counting method, although most of the seaweed patterns are compact. Selected-area ED patterns indicate that the fold stems tilt about 34.5^° around the b-axis and polymer decoration patterns show that the chain folding direction and regularity in two (200) regions are quite different from each other. Because of chain tilting, branched crystals show three striking features: 1) the lamella-like branches show two (200) regions with different thickness; 2) the crystals usually bend towards the thin region; 3) the thick region grows faster by developing branches, thus branches usually occur outside the thick region. The branched patterns show a characteristic width w, which gives a linear relationship with the crystallization temperature on a semilogarithmic plot. Received 15 March 2002 and Received in final form 29 April 2002     

Magnetic properties of the cyclic spincluster Fe6:bicine

The magnetic properties of the cyclic compound [Fe₆(bicine)₆] LiClO₄ ^. 2MeOH are reported. The cluster Fe₆(bicine)₆ forms an antiferromagnetically coupled ring structure of Fe ^III ions. The magnetic susceptibility is measured between 2 and 300 K and yields the exchange coupling of J/k _B = - 27.5±0.5 K. The field dependence of the magnetic moment is studied at 3 and 6 K in magnetic fields up to 5 T. The zero-field splitting of the first excited spin states with S = 2 and 3 are determined by ESR at 94 GHz. The intra-molecular interactions of the Fe ^III ions are analyzed and the on-site anisotropy of the Fe ^III due to the ligand-configuration is determined to d /k _B = - 0.633±0.008K. Received 28 October 2002 / Received in final form 22 February 2003 Published online 20 June 2003 RID="a" ID="a"e-mail: bernd@piobelix.physik.uni-karlsruhe.de     

Electron dynamics in Na and Pt clusters from time-dependent Hartree-Fock theory

We present a method for the numerical investigation of the electron dynamics in small metallic clusters in intense laser fields. We obtain information about collective excitations and relaxation processes in the Na ₉ ⁺ and Pt₃ clusters analyzing the power spectrum of the dipole moment within a mean-field approach. The power spectrum is computed for various laser pulse parameters as well as for the limit of an infinitely short laser pulse. Due to the basis set expansion of the wave function our method is capable to follow the dynamics not only of the whole electron cloud, but of any particular molecular orbital. Received 28 March 2002 / Received in final form 31 May 2002 Published online 24 September 2002 RID="a" ID="a"e-mail: pavlyukh@mpi-halle.de     

Localization-delocalization transition in one-dimensional system with long-range correlated diagonal disorder

We show that the electronic states in a one-dimensional (1D) Anderson model of diagonal disorder with long-range correlation proposed by de Moura and Lyra exhibit localization-delocalization phase transition in varying the energy of electrons. Using transfer matrix method, we calculate the average resistivity and investigate how it changes with the size of the system N. For given value of α (> 2) we find critical energies E_c1 and E_c2 such that the resistivity decreases with N as a power law ∝ N ^{- γ} for electron energies within the range of [E _c1, E _c2], and exponentially grows with N outside this range. Such behaviors persist in approaching the transition points and the exponent γ is in the range from 0.92 to 0.96. The origin of the delocalization in this 1D model is discussed. Received 18 December 2001 / Received in final form 2 May 2002 Published online 14 October 2002 RID="a" ID="a"e-mail: sjxiong@nju.edu.cn