Growth, optical characterization, and laser operation of a stoichiometric crystal KYb(WO4)(2)

We present our recent achievements in the growing and optical characterization of KYb(WO4)2 (hereafter KYbW) crystals and demonstrate laser operation in this stoichiometric material. Single crystals of KYbW with optimal crystalline quality have been grown by the top-seeded-solution growth slow-cooling method. The optical anisotropy of this monoclinic crystal has been characterized, locating the tensor of the optical indicatrix and measuring the dispersion of the principal values of the refractive indices as well as the thermo-optic coefficients. Sellmeier equations have been constructed valid in the visible and near-IR spectral range. Raman scattering has been used to determine the phonon energies of KYbW and a simple physical model is applied for classification of the lattice vibration modes. Spectroscopic studies (absorption and emission measurements at room and low temperature) have been carried out in the spectral region near 1 µm characteristic for the ytterbium transition. Energy positions of the Stark sublevels of the ground and the excited state manifolds have been determined and the vibronic substructure has been identified. The intrinsic lifetime of the upper laser level has been measured taking care to suppress the effect of reabsorption and the intrinsic quantum efficiency has been estimated. Lasing has been demonstrated near 1074 nm with 41% slope efficiency at room temperature using a 0.5 mm thin plate of KYbW. This laser material holds great promise for diode pumped high-power lasers, thin disk and waveguide designs as well as for ultrashort (ps/fs) pulse laser systems.

Calorimetry of hydrogen desorption from a-Si nanoparticles

The process of hydrogen desorption from amorphous silicon (a-Si) nanoparticles grown by plasma-enhanced chemical vapor deposition (PECVD) has been analyzed by differential scanning calorimetry (DSC), mass spectrometry, and infrared spectroscopy, with the aim of quantifying the energy exchanged. Two exothermic peaks centered at 330 and 410 C have been detected with energies per H atom of about 50 meV. This value has been compared with the results of theoretical calculations and is found to agree with the dissociation energy of Si-H groups of about 3.25 eV per H atom, provided that the formation energy per dangling bond in a-Si is about 1.15 eV. It is shown that this result is valid for a-Si:H films, too.

Performance of correlation functionals in ab initio chemisorption cluster-model calculations: Alkali metals on Si(111)

The performance of different correlation functionals has been tested for alkali metals, Li to Cs, interacting with cluster models simulating different active sites of the Si(111) surface. In all cases, the ab initio Hartree-Fock density has been obtained and used as a starting point. The electronic correlation energy is then introduced as an a posteriori correction to the Hartree-Fock energy using different correlation functionals. By making use of the ionic nature of the interaction and of different dissociation limits we have been able to prove that all functionals tested introduce the right correlation energy, although to a different extent. Hence, correlation functionals appear as an effective and easy way to introduce electronic correlation in the ab initio Hartree-Fock description of the chemisorption bond in complex systems where conventional configuration interaction techniques cannot be used. However, the calculated energies may differ by some tens of eV. Therefore, these methods can be employed to get a qualitative idea of how important correlation effects are, but they have some limitations if accurate binding energies are to be obtained.

Neutral atoms in ionic lattices: Excited states of KCl:Ag(0)

The optical-absorption spectrum of a cationic Ag0 atom in a KCl crystal has been studied theoretically by means of a series of cluster models of increasing size. Excitation energies have been determined by means of a multiconfigurational self-consistent field procedure followed by a second-order perturbation correlation treatment. Moreover results obtained within the density-functional framework are also reported. The calculations confirm the assignment of bands I and IV to transitions of the Ag-5s electron into delocalized states with mainly K-4s,4p character. Bands II and III have been assigned to internal transitions on the Ag atom, which correspond to the atomic Ag-4d to Ag-5s transition. We also determine the lowest charge transfer (CT) excitation energy and confirm the assignment of band VI to such a transition. The study of the variation of the CT excitation energy with the Ag-Cl distance R gives additional support to a large displacement of the Cl ions due to the presence of the Ag0 impurity. Moreover, from the present results, it is predicted that on passing to NaCl:Ag0 the CT onset would be out of the optical range while the 5s-5p transition would undergo a redshift of 0.3 eV. These conclusions, which underline the different character of involved orbitals, are consistent with experimental findings. The existence of a CT transition in the optical range for an atom inside an ionic host is explained by a simple model, which also accounts for the differences with the more common 3d systems. The present study sheds also some light on the R dependence of the s2-sp transitions due to s2 ions like Tl+.

Adsorption energy and spin state of first-row transition metals adsorbed on MgO(100)

Slab and cluster model spin-polarized calculations have been carried out to study various properties of isolated first-row transition metal atoms adsorbed on the anionic sites of the regular MgO(100) surface. The calculated adsorption energies follow the trend of the metal cohesive energies, indicating that the changes in the metal-support and metal-metal interactions along the series are dominated by atomic properties. In all cases, except for Ni at the generalized gradient approximation level, the number of unpaired electron is maintained as in the isolated metal atom. The energy required to change the atomic state from high to low spin has been computed using the PW91 and B3LYP density-functional-theory-based methods. PW91 fails to predict the proper ground state of V and Ni, but the results for the isolated and adsorbed atom are consistent within the method. B3LYP properly predicts the ground state of all first-row transition atom the high- to low-spin transition considered is comparable to experiment. In all cases, the interaction with the surface results in a reduced high- to low-spin transition energy.

Adsoption-induced restructuring of gold nanochains

The chemical properties of single-atomic chains of gold atoms are investigated using density functional calculations. The nanochains are shown to be unusually chemically active with strong chemisorption of oxygen atoms and carbon monoxide. The chemisorption energies vary significantly with the strain/stress conditions for the chain. Oxygen atoms are found to energetically prefer to get incorporated into a chain forming a new type of gold-oxygen nanochain with a conductance of one quantum unit. We suggest that the long bond lengths observed in electron microscopy investigations of gold chains can be due to oxygen incorporation.

Surface structure and stability of PdZn and PtZn alloys: Density-functional slab model studies

Geometric parameters of binary (1:1) PdZn and PtZn alloys with CuAu-L10 structure were calculated with a density functional method. Based on the total energies, the alloys are predicted to feature equal formation energies. Calculated surface energies of PdZn and PtZn alloys show that (111) and (100) surfaces exposing stoichiometric layers are more stable than (001) and (110) surfaces comprising alternating Pd (Pt) and Zn layers. The surface energy values of alloys lie between the surface energies of the individual components, but they differ from their composition weighted averages. Compared with the pure metals, the valence d-band widths and the Pd or Pt partial densities of states at the Fermi level are dramatically reduced in PdZn and PtZn alloys. The local valence d-band density of states of Pd and Pt in the alloys resemble that of metallic Cu, suggesting that a similar catalytic performance of these systems can be related to this similarity in the local electronic structures.

First principles LDA+U and GGA+U study of cerium oxides: Dependence on the effective U-parameter

The electronic structure and properties of cerium oxides (CeO2 and Ce2O3) have been studied in the framework of the LDA+U and GGA(PW91)+U implementations of density functional theory. The dependence of selected observables of these materials on the effective U parameter has been investigated in detail. The examined properties include lattice constants, bulk moduli, density of states, and formation energies of CeO2 and Ce2O3. For CeO2, the LDA+U results are in better agreement with experiment than the GGA+U results whereas for the computationally more demanding Ce2O3 both approaches give comparable accuracy. Furthermore, as expected, Ce2O3 is much more sensitive to the choice of the U value. Generally, the PW91 functional provides an optimal agreement with experiment at lower U energies than LDA does. In order to achieve a balanced description of both kinds of materials, and also of nonstoichiometric CeO2¿x phases, an appropriate choice of U is suggested for LDA+U and GGA+U schemes. Nevertheless, an optimum value appears to be property dependent, especially for Ce2O3. Optimum U values are found to be, in general, larger than values determined previously in a self-consistent way.

Importance of the embedding environment on the strain within small rings in siliceous materials

The effect of the local environment on the energetic strain within small (SiO)N rings (with N=2,3) in silica materials is investigated via periodic model systems employing density functional calculations. Through comparison of the energies of various nonterminated systems containing small rings in strained and relatively unstrained environments, with alpha quartz, we demonstrate how small ring strain is affected by the nature of the embedding environment. We compare our findings with numerous previously reported calculations, often predicting significantly different small-ring strain energies, leading to a critical assessment of methods of calculating accurate localized ring energies. The results have relevance for estimates of the strain-induced response (e.g., chemical, photo, and radio) of small silica rings, and the propensity for them to form in bulk glasses, thin films, and nanoclusters.

Two and three nucleon induced photon absorption

We have investigated the mechanisms leading to two and three body photon absorption in nuclei. At photon energies around the pion production threshold we obtain a fraction of three body absorption of less than 10% of the total, contradicting previous theoretical claims that it dominates the absorption process. The strength of the three body channel grows smoothly with the photon energy reaching a maximum of about 60% of the total direct absorption at energies of the photon around 400 MeV.

Relativistic Thomas-Fermi description of collective modes in droplets of nuclear matter

Isoscalar collective modes in a relativistic meson-nucleon system are investigated in the framework of the time-dependent Thomas-Fermi method. The energies of the collective modes are determined by solving consistently the dispersion relations and the boundary conditions. The energy weighted sum rule satisfied by the models considered allows the identification of the giant resonances. The percentage of the energy weighted sum rule exhausted by the collective modes is in agreement with experimental data, but the agreement with the energy of the modes depends on the model considered.

High-momentum proton removal from 16 O and the (e,e'p) cross section

The cross section for the removal of high-momentum protons from 16O is calculated for high missing energies. The admixture of high-momentum nucleons in the 16O ground state is obtained by calculating the single-hole spectral function directly in the finite nucleus with the inclusion of short-range and tensor correlations induced by a realistic meson-exchange interaction. The presence of high-momentum nucleons in the transition to final states in 15N at 60¿100 MeV missing energy is converted to the coincidence cross section for the (e,e¿p) reaction by including the coupling to the electromagnetic probe and the final state interactions of the outgoing proton in the same way as in the standard analysis of the experimental data. Detectable cross sections for the removal of a single proton at these high missing energies are obtained which are considerably larger at higher missing momentum than the corresponding cross sections for the p-wave quasihole transitions. Cross sections for these quasihole transitions are compared with the most recent experimental data available.

Delta(1232) isobar excitations and the ground state of nuclei

The influence of Delta isobar components on the ground-state properties of nuclear systems is investigated for nuclear matter as well as finite nuclei. Many-body wave functions, including isobar configurations and binding energies, are evaluated employing the framework of the coupled-cluster theory. It is demonstrated that the effect of isobar configurations depends in a rather sensitive way on the model used for the baryon-baryon interaction. As examples for realistic baryon-baryon interactions with explicit inclusion of isobar channels we use the local (V28) and nonlocal meson-exchange potentials (Bonn2000) but also a model recently developed by the Salamanca group, which is based on a quark picture. The differences obtained for the nuclear observables are related to the treatment of the interaction, the pi-exchange contributions in particular, at high momentum transfers.

Superheavy nuclei in relativistic effective Lagrangian model

Isotopic and isotonic chains of superheavy nuclei are analyzed to search for spherical double shell closures beyond Z=82 and N=126 within the new effective field theory model of Furnstahl, Serot, and Tang for the relativistic nuclear many-body problem. We take into account several indicators to identify the occurrence of possible shell closures, such as two-nucleon separation energies, two-nucleon shell gaps, average pairing gaps, and the shell correction energy. The effective Lagrangian model predicts N=172 and Z=120 and N=258 and Z=120 as spherical doubly magic superheavy nuclei, whereas N=184 and Z=114 show some magic character depending on the parameter set. The magicity of a particular neutron (proton) number in the analyzed mass region is found to depend on the number of protons (neutrons) present in the nucleus.

Entropy of a correlated system of nucleons

Realistic nucleon-nucleon interactions induce correlations to the nuclear many-body system, which lead to a fragmentation of the single-particle strength over a wide range of energies and momenta. We address the question of how this fragmentation affects the thermodynamical properties of nuclear matter. In particular, we show that the entropy can be computed with the help of a spectral function, which can be evaluated in terms of the self-energy obtained in the self-consistent Green's function approach. Results for the density and temperature dependences of the entropy per particle for symmetric nuclear matter are presented and compared to the results of lowest order finite-temperature Brueckner-Hartree-Fock calculations. The effects of correlations on the calculated entropy are small, if the appropriate quasiparticle approximation is used. The results demonstrate the thermodynamical consistency of the self-consistent T-matrix approximation for the evaluation of the Green's functions.