Photophysics of C<Subscript>60</Subscript> and C<Subscript><Emphasis Type="Bold">60</Emphasis></Subscript><Superscript><Emphasis Type="Bold">-</Emphasis></Superscript> in faujasite zeolites

While the intercalation of C₆₀ and the formation of C ₆₀ ^- in the supercages of NaX and NaY are confirmed by using ¹²⁹Xe NMR and ESR, the photophysical properties of C₆₀ and C ₆₀ ^- are characterized by monitoring transient reflectance spectra and kinetics, fluorescence kinetics, and diffuse reflectance spectra. C ₆₀ ^- is considerably more abundant in NaY than in NaX. This difference is explained in terms of polarity difference between two zeolites. Both C₆₀ and C ₆₀ ^- have remarkably elongated excited-state lifetimes due to their collision-free environment in zeolitic nanocavities although C ₆₀ ^- has much shorter lifetimes than C₆₀. C ₆₀ ^- , in particular, shows intense absorption and emission due to its reduced symmetry in zeolites. Received 13 July 2001 and Received in final form 8 October 2001     

Photoexcitation of rare-gas neon and argon clusters doped with <Emphasis Type="Bold">H</Emphasis><Subscript><Emphasis Type="Bold">2</Emphasis></Subscript><Emphasis Type="Bold">O</Emphasis>

We have studied the fluorescence of electronically excited OH^*, H^* and H₂O^+* dissociation fragments after VUV excitation ( h ν≥11.6 eV) of rare-gas clusters (Rg = Ne, Ar) doped with H₂O molecules. In contrast to a free molecule, where Balmer H-series dominate the UV-visible spectra, only the OH ^* ( A ² Σ ⁺ ↦ X ² Π) emission band is observed in neon clusters. No emission of excited water ions has been observed. We find that while higher excitation energies (Ne vs. Ar) induce higher vibrational excitation of the OH^* ( A ) fragment, the rotational temperature is lower. This effect is attributed to the difference in the geometric position of the H₂O molecule on the surface or inside the Rg-cluster. The rotational relaxation in neon clusters is rapid while the vibrational relaxation is slow because of the coupling with the low energy matrix phonons. Received 7 March 2002 / Received in final form 27 May 2002 Published online 19 July 2002     

Magnetic properties of LaNi <Emphasis Type="Bold">1-</Emphasis><Emphasis Type="Bold">x</Emphasis>Mn <Emphasis Type="Bold">x</Emphasis>O <Emphasis Type="Bold">3+δ</Emphasis> perovskites

Magnetic measurements have been carried out in different LaNi_1-xMn_xO _{3 + δ} samples with 0.1 ⩽ x ⩽ 0.9. All these samples show two magnetic anomalies, one at relatively high temperature characteristic of a ferromagnetic ordering and the other at low temperature, typical of magnetic relaxation phenomena. Neutron diffraction patterns indicate that long-range ferromagnetic ordering is only achieved for x ≥ 0.5. Neutron patterns of LaNi_0.5Mn_0.5O _{3 + δ} samples show an ordered arrangement of Ni and Mn atoms in the perovskite lattice. LaNi_0.5Mn_0.5O _{3 + δ} is then, a double perovskite A₂BB'O₆ whereas Ni and Mn atoms are randomly distributed for the rest of the samples. X-ray magnetic circular dichroism experiments confirm the presence of collinear ferromagnetism in LaNi_0.5Mn_0.5O _{3 + δ} . The role of competitive magnetic interactions, structural disorder, magnetic anisotropy and magnetic disaccommodation is also discussed Received 19 July 2002 / Received in final form 23 October 2002 Published online 31 December 2002     

Giant magneto-optical response of ferromagnetic EuB<Subscript><Emphasis Type="Bold">6</Emphasis></Subscript>

Intercalation of polyatomic molecules into a superconductor can drastically affect the properties of the compound. A mechanism responsible for a large increase in T _c for such systems is proposed. It explains the recent remarkable observation of high T _c superconductivity in the hole-doped C₆₀/CHX₃ (X≡Cl, Br) compounds and the large shift in their T _c upon Cl↦Br substitution. The increase in T _c is due to contribution to the pairing arising from the interaction of electrons with the vibrational manifold of the molecule. The proposed mechanism opens up the possibility to observe a site-selective isotope effect. We also suggest that intercalating CHI₃ would further increase the critical temperature to T _c≃ 140 K. Received 23 January 2002     

<Emphasis Type="Italic">Comment on</Emphasis>¶Low temperature specific heat of blue bronze K <Emphasis Type="Bold">0.30</Emphasis>MoO <Emphasis Type="Bold">3</Emphasis>, by J. Odin,J.C. Lasjaunias,K. Biljaković, K. Hasselbach,and P. Monceau

Eur. Phys. J. B 24, 315 (2001) Here we comment on a recently published paper on the presence of a phason contribution in the low temperature heat capacity data of the charge-density-wave compounds K_0.3MoO₃ and (TaSe₄)₂I. We have shown that the anomaly in the C _P / T ³ data reported by Odin et al. is straightforwardly interpreted in terms of low energy phonon modes resulting from the peculiar topology of these compounds. Received 21 February 2002 Published online 19 July 2002     

Strain effect on transport properties of <Emphasis Type="Bold">SrRuO</Emphasis><Subscript><Emphasis Type="Bold">3</Emphasis></Subscript> films grown by laser MBE

Transport properties of SrRuO₃ thin films were studied as a function of the epitaxial strain. SrRuO₃ films were grown on (100) SrTiO₃ substrates by the Pulsed Laser Deposition technique equipped with Reflection High Energy Electrons Diffraction (RHEED). Samples thickness has been varied from a few unit cells to above 1000 ? while monitoring RHEED intensity oscillations. In thicker films epitaxial strain was found to be progressively relaxed. SrRuO₃ relaxed films (thickness 1000 ?) show metallic behavior for the whole temperature range with a ferromagnetic ordering at about 150 K. For thinner films, ferromagnetic ordering occurs at progressively lower temperatures, until in films thinner than 400 ? it disappears. Films thinner than 80 ? show a semiconducting behavior at low temperatures. Our results provide direct evidence of the crucial role of the strain effect for conducting and magnetic properties of SrRuO₃. Received 16 July 2001 and Received in final form 22 October 2001     

Laser-induced fluorescence study of the influence of N <Emphasis Type="Bold">2</Emphasis> and CH <Emphasis Type="Bold">4</Emphasis> on the <Emphasis Type="Bold">114</Emphasis>Cd intercombination line

Using a laser-induced fluorescence method a detailed analysis of profiles of the ¹¹⁴Cd 326.1 nm line perturbed by N₂ and CH₄ was performed which revealed deviations from the ordinary Voigt profile. These deviations are shown to be consistent with fits of experimental profiles to an asymmetric Voigt profile. Coefficients of the pressure broadening, shift and collision-time asymmetry are determined and compared with those calculated for van der Waals interaction potential. Received 29 November 2001 / Received in final form 12 July 2002 Published online 4 February 2003     

Isomerization and dissociation of small (CH <Emphasis Type="Bold">3</Emphasis>CN) <Emphasis Type="Bold">n</Emphasis> molecular clusters: a computational study

The isomerization and evaporation processes in the neutral homogeneous (CH₃CN)_n molecular clusters (n = 2-7) have been investigated using classical molecular dynamics simulations. The evaporation rate constants and the kinetic energy release in the dissociation have been analysed as a function of the cluster size and as a function of the internal energy in the parent cluster. The competition between monomer and dimer ejections has been also carefully studied. All the dynamical properties in these dissociative processes have been discussed in relation to the static properties of the clusters involved in the dissociation and also in relation to the solid-liquid like transition which appears in these homogeneous molecular clusters. Received 19 November 2002 / Received in final form 5 February 2003 Published online 29 April 2003 RID="a" ID="a"e-mail: pascal.parneix@ppm.u-psud.fr RID="b" ID="b"Laboratoire associé à l'université Paris-Sud.     

Metastability of gold-carbonyl cluster complexes, Au N(CO) M -

Smaller gold-cluster anions, typified by Au ₇ ^- , adsorb multiple CO molecules in a high-pressure, room-temperature flow-reactor, tending toward previously unknown saturation compositions, Au₇(CO) ₄ ^- . The weakness of the gold-carbonyl adsorption bond is evidenced indirectly by the high CO partial pressure required and more directly by the high probability of fragmentation in the field-free flight region of the reflectron-type time-of-flight mass spectrometer. The analysis of this metastability reveals that the actual distribution f_N,M of products Au₇(CO) _M ^- in the reactor may be highly non-statistical, e.g. with only even-M species present. Received 17 April 2001     

Tight-binding study of structural and electronic properties of silver clusters

Tight-binding model is developed to study the structural and electronic properties of silver clusters. The ground state structures of Ag clusters up to 21 atoms are optimized by molecular dynamics-based genetic algorithm. The results on small Ag_n clusters (n = 3-9) are comparable to ab initio calculations. The size dependence of electronic properties such as density of states, s-d band separation, HOMO-LUMO gap, and ionization potentials are discussed. Magic number behavior at Ag₂, Ag₈, Ag₁₄, Ag₁₈, Ag₂₀ is obtained, in agreement with the prediction of electronic ellipsoid shell model. We suggest that both the electronic and geometrical effect play significant role in the coinage metal clusters. Received 7 August 2000     

Assembling of hydrogenated aluminum clusters

The electronic and atomic structure of Al₁₃H has been studied using Density Functional Theory. Al₁₃H has closed electronic shells. This makes the cluster very stable and suggests that it could be a candidate to form cluster assembled solids. The interaction between two Al₁₃H clusters was analyzed and we found that the two units preserve their identities in the dimer. A cubic-like solid phase assembled from Al₁₃H units was then modeled. In that solid the clusters retain much of their identity. Molecular dynamics runs show that the structure of the assembled solid is stable at least up to 150 K. A favorable relative orientation of the clusters with respect to their neighbors is critical for the stability of that solid. Received 21 November 2000     

Study of (Al2O3)n(Ox) clusters with n = 16 and x = 0, 1, 2 from first principles calculations

The ionic and electronic structure of (Al₂O₃)_n(O_x) clusters with n 16 and x = 0, 1, 2 is studied by means of first principles density functional calculations, norm-conserving pseudopotentials and a numerical atomic basis set. The equilibrium geometries have been determined by total energy minimization, starting with several initial geometries for each cluster size. The trends obtained for the atomic arrangements (structural isomers, coordination numbers, disordered versus ordered structures, etc.) and the electronic properties (binding energies, Homo-Lumo gap and dipole moments) are discussed. For most of the oxidized clusters studied here we find that the Homo-Lumo gap and the magnitude of dipole moment of isomeric species can vary drastically.     

Electron-electron bound states in Maxwell-Chern-Simons-Proca QED <Emphasis Type="Bold">3</Emphasis>

We start from a parity-breaking MCS QED₃ model with spontaneous breaking of the gauge symmetry as a framework for evaluation of the electron-electron interaction potential and for attainment of numerical values for the e ^- e ^- - bound state. Three expressions ( V _eff , V _eff , V _eff ) are obtained according to the polarization state of the scattered electrons. In an energy scale compatible with condensed matter electronic excitations, these three potentials become degenerated. The resulting potential is implemented in the Schr?dinger equation and the variational method is applied to carry out the electronic binding energy. The resulting binding energies in the scale of 10-100 meV and a correlation length in the scale of 10-30 ? are possible indications that the MCS-QED₃ model adopted may be suitable to address an eventual case of e ^- e ^- pairing in the presence of parity-symmetry breakdown. The data analyzed here suggest an energy scale of 10-100 meV to fix the breaking of the U (1)-symmetry. Received 24 September 2002 / Received in final form 15 January 2003 Published online 1st April 2003 RID="a" ID="a"e-mail: belich@cbpf.br RID="b" ID="b"e-mail: delcima@cbpf.br RID="c" ID="c"e-mail: manojr@cbpf.br RID="d" ID="d"e-mail: helayel@cbpf.br     

Competing polarization mechanisms in the heavy-fermion paramagnet CeCu<Subscript><Emphasis Type="Bold">6</Emphasis></Subscript>

Nuclear magnetic resonance (NMR) and relaxation of ⁶³Cu and ⁶⁵Cu in a powder sample of the heavy-fermion paramagnet CeCu₆ is measured and analysed quantitatively. Five different Cu sites are accessible to a detailed analysis. We derive quadrupolar splitting frequencies, Ce to Cu transferred hyperfine field coupling constants, and transversal as well as longitudinal relaxation behaviour. Only small relaxation anomalies are observed at the orthorhombic to monoclinic structural phase transition of CeCu₆. We point to the different importance of transferred hyperfine interaction and local conduction electron density for static or dynamic part, respectively, of Cu hyperfine interaction. The different sign of the transferred hyperfine interaction from Ce³⁺ to different Cu neighbours reveals the different competing interaction mechanisms, giving rise to the heavy-fermion paramagnetic behavior of CeCu₆. Received 20 November 2001     

Covalent magnetism in the RFe <Emphasis Type="Bold">6</Emphasis>Ge <Emphasis Type="Bold">6</Emphasis> series

The electronic structure of the RFe ₆ Ge ₆ compounds ( R = Sc, Lu, Ti, Zr, Hf and Nb) of HfFe ₆ Ge ₆ -type structure has been studied using the muffin-tin Korringa-Kohn-Rostoker method in a non-relativistic approach. The chemical bonding is analyzed based on the l-decomposed site projected densities of states. Spin-dependent changes in the R nd- Fe 3d covalent bond are shown to be responsible for the experimentally observed rise in the Fe moment and hyperfine field upon increasing the R valency. The limited quantitative agreement between theoretical and experimental values is interpreted as being due to a non-negligible orbital moment and to a significant asphericity in the spin density at the iron site. The theoretical results also forecast a strong increase of the Ge(2e) transferred hyperfine field with the R valency. Received 20 December 2002 Published online 4 June 2003 RID="a" ID="a"e-mail: Thomas.Mazet@lcsm.uhp-nancy.fr RID="b" ID="b"Associé au CNRS (UMR 7555)     

Self-assembly of Mo<Subscript> 6</Subscript>S<Subscript> 8</Subscript> clusters on the Au(111) surface

The preferred adsorption sites and the propensity for a self-organised growth of the molybdenum sulfide cluster Mo₆S₈ on the Au(111) surface are investigated by density-functional band-structure calculations with pseudopotentials and a plane wave basis set. The quasi-cubic cluster preferentially adsorbs via a face and remains structurally intact. It experiences a strong, mostly non-ionic attraction to the surface at several quasi-isoenergetic adsorption positions. A scan of the potential energy surface exhibits only small barriers between adjacent strong adsorption sites. Hence, the cluster may move in a potential well with degenerate local energy minima at room temperature. The analysis of the electronic structure reveals a negligible electron transfer and S-Au hybridised states, which indicate that the cluster-surface interaction is dominated by S-Au bonds, with minor contributions from the Mo atom in the surface vicinity. All results indicate that Mo₆S₈ clusters on the Au(111) surface can undergo a template-mediated self-assembly to an ordered inorganic monolayer, which is still redox active and may be employed as surface-active agent in the integration of noble metal and ionic or biological components within nano-devices. Therefore, a classical potential model was developed on the basis of the DFT data, which allows to study larger cluster assemblies on the Au(111).     

Magnetism in Rh clusters under hydrostatic deformations

The magnetic behavior of rhodium clusters Rh_N (N = 4-38) under hydrostatic deformations was investigated. The starting cluster structures were obtained from an evolutionary search algorithm applied to a Gupta potential. The spin-polarized electronic structure and related magnetic properties were calculated using a self-consistent spd tight-binding Hamiltonian within the unrestricted Hartree-Fock approximation. The magnetic behavior was analyzed in terms of the interdependence between the geometrical parameters and the electronic structure. Anomalous magnetic effects were found in some cases. Received 5 August 2002 / Received in final form 10 January 2003 Published online 4 March 2003 RID="a" ID="a"e-mail: berlanga@dec1.ifisica.uaslp.mx     

Low-temperature specific heat of Sr<Subscript>2</Subscript>RuO<Subscript>4</Subscript>

We report low-temperature measurements 0.07 K ? T ? 2 K of the specific heat, C, of the perovskite superconductor Sr₂RuO₄. Based on a detailed analysis of our data with respect to both sample quality (as measured by T _c = 0.43 K - 1.17 K) and magnetic-field dependence, it is shown that the electronic contribution to the specific heat, which contains the desired information on the gap structure, is superimposed by at least two additional contributions: a Schottky-type hump at T ≈ 0.1 - 0.2 K and a low-temperature upturn in C / T at T < 0.1 K. We discuss possible origins of these additional contributions and their implications for the interpretation of low-temperature C ( T ) data. Received 23 August 2001     

Novel metal-encapsulated caged clusters of silicon and germanium

We report the recent findings of metal (M) encapsulated clusters of silicon from computer experiments based on ab initio total energy calculations and a cage shrinkage and atom removal approach. Our results show that using a guest atom, it is possible to wrap silicon in fullerenelike (f) structures, as sp² bonding is not favorable to produce empty cages unlike for carbon. Transition M atoms have a strong bonding with the silicon cage that are responsible for the compact structures. The size and structure of the cage change from 14 to 20 Si atoms depending upon the size and valence of the M atom. Fewer Si atoms lead to relatively open structures. We find cubic, f, Frank-Kasper (FK) polyheral type, decahedral, icosahedral and hexagonal structures for M@Si_n with n = 12-16 and several different M atoms. The magic behavior of 15 and 16 atom Si cages is in agreement with experiments. The FK polyhedral cluster, M@Si₁₆ has an exceptionally large density functional gap of about 2.35 eV calculated within the generalized gradient approximation. It is likely to give rise to visible luminescence in these clusters. The cluster-cluster interaction is weak that makes such clusters attractive for cluster assembled materials. Further studies to stabilize Si₂₀ cage with M = Zr, Ba, Sr, and Pb show that in all cases there is a distortion of the f cage. Similar studies on M encapsulated germanium clusters show FK polyhedral and decahedral isomers to be more favorable. Also perfect icosahedral M@Ge₁₂ and M@Sn₁₂ clusters have been obtained with large gaps by doping with divalent M atoms. Recent results of the H interaction with these clusters, hydrogenated silicon fullerenes as well as assemblies of clusters such as nanowires and nanotubes are briefly presented.     

Photoionization and detection of ultracold Cs<Subscript><Emphasis Type="Bold">2</Emphasis></Subscript> molecules through diffuse bands

We present the results of absorption measurements in a cesium vapor around 630 K, together with photoionization spectra through a resonance-enhanced two-photon absorption of ultracold cesium dimers created after photoassociation of ultracold cesium atoms. The maximum efficiency of the ultracold molecule ionization is found for wavelengths where absorption at thermal energies is the strongest, in agreement with our theoretical simulations of both processes, involving the so-called Cs₂ diffuse bands. This result will be helpful for further optimization of such a direct way of detection of ultracold molecules. Received 13 September 2001