Low-lying singlet and triplet electronic states of RhB

The low-lying X-1 Sigma(+), a(3)Delta, A(1)Delta, b(3)Sigma(+), B-1 Pi, c(3)Pi, C-1 Phi, D-1 Sigma(+), E-1 Pi, d(1)Phi, and e(3)Pi electronic states of RhB have been investigated at the ab initio level, using the multistate multiconfigurational second-order perturbation (MS-CASPT2) theory, with extended atomic basis sets and inclusion of scalar relativistic effects. Among the eleven electronic states included in this work, only three (the X-1 Sigma(+), D-1 Sigma(+), and E-1 Pi states) have been investigated experimentally. Potential energy curves, spectroscopic constants, dipole moments, binding energies, and chemical bonding aspects are presented for all electronic states.

A theoretical study of the binding and electronic spectrum of the Mo-2 molecule

Multiconfigurational SCF and second-order perturbation theory have been employed to study seven low-lying singlet and triplet electronic states of the Mo-2 molecule. The bond order of the ground state has been analyzed based on the effective bond order (EBO), indicating that a fully developed sextuple bond is formed between the two Mo atoms. The experimentally observed excited states a(3)Sigma(+)(u) and A(1)Sigma(+)(u) have been determined and the so-called (3)Lambda excited state identified as the b(3)Sigma(+)(u) state, in agreement with experimental expectations. (C) 2007 Elsevier B.V. All rights reserved.

Axial ligand influence on geometries, charge distributions and electronic structures of iron tetraazamacrocycle [Fe((II))TIM(X)(Y)](2+) complexes assessed by Density Functional Theory

We employed the Density Functional Theory along with small basis sets, B3LYP/LANL2DZ, for the study of FeTIM complexes with different pairs of axial ligands (CO, H(2)O, NH(3), imidazole and CH(3)CN). These calculations did not result in relevant changes of molecular quantities as bond lengths, vibrational frequencies and electronic populations supporting any significant back-donation to the carbonyl or acetonitrile axial ligands. Moreover, a back-donation mechanism to the macrocycle cannot be used to explain the observed changes in molecular properties along these complexes with CO or CH(3)CN. This work also indicates that complexes with CO show smaller binding energies and are less stable than complexes with CH(3)CN. Further, the electronic band with the largest intensity in the visible region (or close to this region) is associated to the transition from an occupied 3d orbital on iron to an empty pi* orbital located at the macrocycle. The energy of this Metal-to-Ligand Charge Transfer (MLCT) transition shows a linear relation to the total charge of the macrocycle in these complexes as given by Mulliken or Natural Population Analysis (NPA) formalisms. Finally, the macrocycle total charge seems to be influenced by the field induced by the axial ligands. (C) 2011 Elsevier Ltd. All rights reserved.

Structural phase transition study of FePt alloys using ab initio calculation

The FePt alloy undergoes the cubic to tetragonal lattice transformation in the ferromagnetic state. We calculated the electronic structure for both cubic and tetragonal structures using the FPLAPW method with APW + lo. Comparing the density of states of the cubic and tetragonal structures, it is expected that the lattice transformation is caused by the band Jahn-Teller effect. (C) 2009 Elsevier B.V. All rights reserved.

Incommensurate spin-density-wave and metal-insulator transition in the one-dimensional periodic Anderson model

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Structural characterization of phase transition of Al2O3 nanopowders obtained by polymeric precursor method

Nanocrystalline Al(2)O(3)powders have been synthesized by the polymeric precursor method. A study of the evolution of crystalline phases of obtained powders was accomplished through X-ray diffraction, micro-Raman spectroscopy and refinement of the structures through the Rietveld method. The results obtained allow the identification of three steps on the gamma-Al2O3 to alpha-Al2O3 phase transition. The single-phase alpha-Al2O3 Powder was obtained after heat-treatment at 1050 degrees C for 2 h. A study of the morphology of the particles was accomplished through measures of crystallite size, specific surface area and transmission electronic microscopy. The particle size is closely related to gamma-Al2O3 to alpha-Al2O3 phase transition. (c) 2007 Elsevier B.V. All rights reserved.

Electronic ceramics based on polycrystalline SnO2, TiO2 and (Sn xTi1-x)O2 solid solution

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Soliton clusters inducing insulator-to-metal transition in polyacetylene: a Su-Schrieffer-Heeger model study

The Su-Schrieffer-Heeger (SSH) Hamiltonian has been one of most used models to study the electronic structure of polyacetylene (PA) chains. It has been reported in the literature that in the SSH framework a disordered soliton distribution can not produce a metallic regime. However, in this work (using the same SSH model and parameters) we show that this is possible. The necessary conditions for true metals (non-vanishing density of states and extended wavefunctions around the Fermi level) are obtained for soliton concentration higher than 6% through soliton segregation (clustering). These results are consistent with recent experimental data supporting disorder as an essential mechanism behind the high conductivity of conducting polymers. (C) 2001 Elsevier B.V. B.V. All rights reserved.

INSULATOR-TO-METAL TRANSITION IN POLYTHIOPHENE

In the present work, the electronic structure of polythiophene at several doping levels is investigated by the use of the Huckel Hamiltonian with sigma-bond compressibility. Excess charges are assumed to be stored in conformational defects of the bipolaron type. The Hamiltonian matrix elements representative of a bipolaron are obtained from a previous thiophene oligomer calculation, and then transferred to very long chains. Negative factor counting and inverse iteration techniques have been used to evaluate densities of states and wave functions, respectively. Several types of defect distributions were analyzed. Our results are consistent with the following: (i) the bipolaron lattice does not present a finite density of states at the Fermi energy at any doping level; (ii) bipolaron clusters show an insulator-to-metal transition at 8 mol% doping level; (iii) segregation disorder shows an insulator-to-metal transition for doping levels in the range 20-30 mor %.

Thermodynamic aspects of ion intercalation in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds: Application to the Everit's salt/Prussian Blue transition

The K+ reversible processes for ion exchange in KhFek[Fe(CN)(6)](l)center dot mH(2)O host compounds (Prussian Blue) were thermodynamically analyzed. A thermodynamic approach was established and developed based on the consideration of a lattice-gas model where the electronic contribution to the chemical potential is neglected and the ion-host interaction is not considered. The occupation fraction of the intercalation process was calculated from the kinetic parameters obtained through ac-electrogravimetry in a previous paper. In this way, the mass potential transfer function introduces a new way to evaluate the thermodynamic aspect of intercalation. Finally, based on the thermodynamic approach, the energy used to put each K+ ion into the host material was calculated. The values were shown to be in good agreement with the values obtained through transient techniques, for example, cyclic voltammetry. As a result, this agreement between theory and experimental data validates the thermodynamic approach considered here, and for the first time, the thermodynamic aspects of insertion were considered for mixed valence materials.

Electronic spectra, ESR and crystal structure of tetrahedral halocuprates(II). The existence of cations (2tbpo·H+) with a very short hydrogen bond

Two compounds [2tbpo·H+)2[CuCl4]= (yellow) and (2tbpo·H+)2[CuBr4]= (dark purple) (tbpo = tribenzylphosphine oxide) have been prepared and investigated by means of crystal structure, electronic, vibrational and ESR spectra. The crystal structure of the (2tbpo·H+)2[CuCl4]= complex was determined by three-dimensional X-ray diffraction. The compound crystallizes in the space group P42/n with unit-cell dimensions a = 19.585(2), c = 9.883(1)Å, V = 3790 (1)Å3, Z = 2, Dm = 1.303 (flotation) Dx = 1.302 Mg m-3. The structure was solved by direct methods and refined by blocked full-matrix least-squares to R = 0.053 for 2583 observed reflections. Cu(II) is coordinated to four chlorides in a tetrahedral arrangement. Tribenzylphosphine oxide molecules, related by a centre of inversion, are connected by a short hydrogen bridge. Chemical analysis, electronic and vibrational spectra showed that the bromide compound is similar to the chloride one and can be formulated as (2tbpo·H+)2[CuBr4]=. The position of the dd transition bands, the charge transfer bands, the ESR and the vibrational spectra of both complexes are discussed. The results are compared with analogous complexes cited in the literature. © 1983.

Insulator-to-metal transition driven by clustering of solitons in polyacetylene

It's believed that the simple Su-Schrieffer-Heeger Hamiltonian can not predict the insulator to metal transition of transpolyacetylene (t-PA). The soliton lattice configuration at a doping level y=6% still has a semiconductor gap. Disordered distributions of solitons close the gap, but the electronic states around the Fermi energy are localized. However, within the same framework, it is possible to show that a cluster of solitons can produce dramatic changes in the electronic structure, allowing an insulator-to-metal transition.

Metal-insulator transition in Nd1-xEuxNiO 3 compounds

Polycrystalline Nd1-xEuxNiO3 (0≤x≤0.5) compounds were synthesized in order to investigate the character of the metal-insulator (MI) phase transition in this series. Samples were prepared through the sol-gel route and subjected to heat treatments at ∼1000 °C under oxygen pressures as high as 80bar. X-ray diffraction (XRD) and neutron powder diffraction (NPD), electrical resistivity ρ(T), and magnetization M(T) measurements were performed on these compounds. The NPD and XRD results indicated that the samples crystallize in an orthorhombic distorted perovskite structure, space group Pbnm. The analysis of the structural parameters revealed a sudden and small expansion of ∼0.2% of the unit cell volume when electronic localization occurs. This expansion was attributed to a small increase of ∼0.003 of the average Ni-O distance and a simultaneous decrease of ∼-0.5° of the Ni-O-Ni superexchange angle. The ρ(T) measurements revealed a MI transition occurring at temperatures ranging from TMI∼193 to 336K for samples with x ≤ 0 and 0.50, respectively. These measurements also show a large thermal hysteresis in NdNiO3 during heating and cooling processes, suggesting a first-order character of the phase transition at TMI. The width of this thermal hysteresis was found to decrease appreciably for the sample Nd 0.7Eu0.3NiO3. The results indicate that cation disorder associated with increasing substitution of Nd by Eu is responsible for changing the first-order character of the transition in NdNiO3. © 2006 IOP Publishing Ltd.

Accurate ab initio potential energy surfaces for the (3)A '' and (3)A ' electronic states of the O(P-3) plus HBr system

In this work, we report the construction of potential energy surfaces for the (3)A '' and (3)A' states of the system O(P-3) + HBr. These surfaces are based on extensive ab initio calculations employing the MRCI+Q/CBS+SO level of theory. The complete basis set energies were estimated from extrapolation of MRCI+Q/aug-cc-VnZ(-PP) (n = Q, 5) results and corrections due to spin-orbit effects obtained at the CASSCF/aug-cc-pVTZ(-PP) level of theory. These energies, calculated over a region of the configuration space relevant to the study of the reaction O(P-3) + HBr -> OH + Br, were used to generate functions based on the many-body expansion. The three-body potentials were interpolated using the reproducing kernel Hilbert space method. The resulting surface for the (3)A '' electronic state contains van der Waals minima on the entrance and exit channels and a transition state 6.55 kcal/mol higher than the reactants. This barrier height was then scaled to reproduce the value of 5.01 kcal/mol, which was estimated from coupled cluster benchmark calculations performed to include high-order and core-valence correlation, as well as scalar relativistic effects. The (3)A' surface was also scaled, based on the fact that in the collinear saddle point geometry these two electronic states are degenerate. The vibrationally adiabatic barrier heights are 3.44 kcal/mol for the (3)A '' and 4.16 kcal/mol for the (3)A' state. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4705428]

Synthesis, Characterization and Biological Activities of a Bidentate Schiff Base Ligand: N,N '-Bis(1-phenylethylidene)ethane-1,2-diamine and its Transition Metals (II) Complexes

Schiff base ligand: N,N'-bis(1-phenylethylidene)ethane-1,2-diamine (L), was derived from acetophenone and ethylenediamine by condensation and its complexes (1-5) were prepared with Pb2+, Ni2+, Co2+, Cu2+ and Cd2+ metal ions. Their structures were characterized by FAB-MS, IR spectra, elemental analyses and molar conductance. The octahedral geometry of the complexes was proposed by electronic spectra and magnetic moment data. The conductivity data showed that the complexes have non-electrolytic nature. The complexes (1-5) have higher in vitro antimicrobial activity than the Schiff base ligand (L). In the nuclease activity, the complexes cleave DNA as compared to control DNA in the presence of H2O2.