Electronic transitions and bonding properties in a series of five-coordinate “16-electron” complexes [Mn(CO)3(L2)]− (L2=chelating redox-active π-donor ligand)

In this article we present for the first time accurate density functional theory (DFT) and time-dependent (TD) DFT data for a series of electronically unsaturated five-coordinate complexes [Mn(CO)(3)(L-2)](-), where L-2 stands for a chelating strong pi-donor ligand represented by catecholate, dithiolate, amidothiolate, reduced alpha-diimine (1,4-dialkyl-1,4-diazabutadiene (R-DAB), 2,2'-bipyridine) and reduced 2,2'-biphosphinine types. The single-crystal X-ray structure of the unusual compound [Na(BPY)][Mn(CO)(3)(BPY)]center dot Et2O and the electronic absorption spectrum of the anion [Mn(CO)(3)(BPY)](-) are new in the literature. The nature of the bidentate ligand determines the bonding in the complexes, which varies between two limiting forms: from completely pi-delocalized diamagnetic {(CO)(3)Mn-L-2}(-) for L-2 = alpha-diimine or biphosphinine, to largely valence-trapped {(CO)(3)Mn-1-L-2(2-)}(-) for L-2(2-) = catecholate, where the formal oxidation states of Mn and L-2 can be assigned. The variable degree of the pi-delocalization in the Mn(L-2) chelate ring is indicated by experimental resonance Raman spectra of [Mn(CO)(3)(L-2)](-) (L-2=3,5-di-tBu-catecholate and iPr-DAB), where accurate assignments of the diagnostically important Raman bands have been aided by vibrational analysis. The L-2 = catecholate type of complexes is known to react with Lewis bases (CO substitution, formation of six-coordinate adducts) while the strongly pi-delocalized complexes are inert. The five-coordinate complexes adopt usually a distorted square pyramidal geometry in the solid state, even though transitions to a trigonal bipyramid are also not rare. The experimental structural data and the corresponding DFT-computed values of bond lengths and angles are in a very good agreement. TD-DFT calculations of electronic absorption spectra of the studied Mn complexes and the strongly pi-delocalized reference compound [Fe(CO)(3)(Me-DAB)] have reproduced qualitatively well the experimental spectra. Analyses of the computed electronic transitions in the visible spectroscopic region show that the lowest-energy absorption band always contains a dominant (in some cases almost exclusive) contribution from a pi(HOMO) -> pi*(LUMO) transition within the MnL2 metallacycle. The character of this optical excitation depends strongly on the composition of the frontier orbitals, varying from a partial L-2 -> Mn charge transfer (LMCT) through a fully delocalized pi(MnL2) -> pi*(MnL2) situation to a mixed (CO)Mn -> L-2 charge transfer (LLCT/MLCT). The latter character is most apparent in the case of the reference complex [Fe(CO)(3)(Me-DAB)]. The higher-lying, usually strongly mixed electronic transitions in the visible absorption region originate in the three lower-lying occupied orbitals, HOMO - 1 to HOMO - 3, with significant metal-d contributions. Assignment of these optical excitations to electronic transitions of a specific type is difficult. A partial LLCT/MLCT character is encountered most frequently. The electronic absorption spectra become more complex when the chelating ligand L-2, such as 2,2'-bipyridine, features two or more closely spaced low-lying empty pi* orbitals.

A new interpretation of the bonding properties and UV–vis spectra of [M3(CO)12] clusters (M = Ru, Os): a TD-DFT study

DFT and TD-DFT calculations (ADF program) were performed in order to analyze the electronic structure of the [M-3(CO)(12)] clusters (M = Ru, Os) and interpret their electronic spectra. The highest occupied molecular orbitals are M-M bonding (sigma) involving different M-M bonds, both for Ru and Os. They participate in low-energy excitation processes and their depopulation should weaken M-M bonds in general. While the LUMO is M-NI and M-CO anti-bonding (sigma*), the next, higher-lying empty orbitals have a main contribution from CO (pi*) and either a small (Ru) or an almost negligible one (Os) from the metal atoms. The main difference between the two clusters comes from the different nature of these low-energy unoccupied orbitals that have a larger metal contribution in the case of ruthenium. The photochemical reactivity of the two clusters is reexamined and compared to earlier interpretations.

Bubbling transition to spatial mode excitation in an extended dynamical system

We investigated the transition to spatio-temporal chaos in spatially extended nonlinear dynamical systems possessing an invariant subspace with a low-dimensional attractor. When the latter is chaotic and the subspace is transversely stable we have a spatially homogeneous state only. The onset of spatio-temporal chaos, i.e. the excitation of spatially inhomogeneous modes, occur through the loss of transversal stability of some unstable periodic orbit embedded in the chaotic attractor lying in the invariant subspace. This is a bubbling transition, since there is a switching between spatially homogeneous and nonhomogeneous states with statistical properties of on-off intermittency. Hence the onset of spatio-temporal chaos depends critically both on the existence of a chaotic attractor in the invariant subspace and its being transversely stable or unstable. (C) 2008 Elsevier B.V. All rights reserved.

Electronic properties of liquid hydrogen fluoride: A sequential quantum mechanical/Born-Oppenheimer molecular dynamics approach

The electronic properties of liquid hydrogen fluoride (HF) were investigated by carrying out sequential quantum mechanics/Born-Oppenheimer molecular dynamics. The structure of the liquid is in good agreement with recent experimental information. Emphasis was placed on the analysis of polarisation effects, dynamic polarisability and electronic excitations in liquid HF. Our results indicate an increase in liquid phase of the dipole moment (similar to 0.5 D) and isotropic polarisability (5%) relative to their gas-phase values. Our best estimate for the first vertical excitation energy in liquid HF indicates a blue-shift of 0.4 +/- 0.2 eV relative to that of the gas-phase monomer (10.4 eV). (C) 2010 Elsevier B.V. All rights reserved.

Electronic properties of a methane-water solution

Electronic properties of a methane-water solution were investigated by a sequential quantum mechanical/molecular dynamics approach. Upon hydration methane acquires an induced dipole moment of similar to 0.5 +/- 0.2 D. This is related to polarisation effects and to weak methane-water hydrogen bond interactions. From gas phase to solution, the first vertical excitation and ionisation energies of methane are red-shifted by 0.45 +/- 0.25 and 0.87 +/- 0.40 eV, respectively. We also report results for the dynamic polarisability of methane in water. In comparison with water, no difference was found for the average monomeric dipole moment of water molecules in close interaction with methane. (c) 2011 Elsevier B.V. All rights reserved.

MAGNETIC FIELD INDUCED NEAR-BAND-GAP OPTICAL PROPERTIES IN EuTe LAYERS

The magnetic response of the near-band-edge optical properties is studied in EuTe layers. In several magneto-optical experiments, the absorption and emission are described as well as the related Stokes shift. Specifically, we present the first experimental report of the photoluminescence excitation (PLE) spectrum in Faraday configuration. The PLE spectra shows to be related with the absorption spectra through the observation of resonance between the excitation light and the zero-field band-gap. A new emission line appears at 1.6 eV at a moderate magnetic field in the photoluminescence (PL) spectra. Furthermore, we examine the absorption and PL red-shift induced by the magnetic field in the light of the d-f exchange interaction energy involved in these processes. Whereas the absorption red-shift shows a quadratic dependence on the field, the PL red-shift shows a linear dependence which is explained by spin relaxation of the excited state.

Structural and optical properties on thulium-doped LHPG-grown Ta(2)O(5) fibres

Structural, spectroscopic and dielectric properties of thulium-doped laser-heated pedestal Ta(2)O(5) as-grown fibres were studied. Undoped samples grow preferentially with a single crystalline monoclinic structure. The fibre with the lowest thulium content (0.1 at%) also shows predominantly a monoclinic phase and no intra-4f(12) Tm(3+) recombination was observed. For sample with the highest thulium amount (1.0 at%), the appearance of a dominant triclinic phase as well as intraionic optical activation was observed. The dependence of photoluminescence on excitation energy allows identification of different site locations of Tm(3+) ions in the lattice. The absence of recombination between the first and the ground-state multiplets as well as the temperature dependence of the observed transitions was justified by an efficient energy transfer between the Tm(3+) ions. Microwave dielectric properties were investigated using the small perturbation theory. At a frequency of 5 GHz, the undoped material exhibits a dielectric permittivity of 21 and for thulium-doped Ta(2)O(5) samples it decreases to 18 for the highest doping concentration. Nevertheless, the dielectric losses maintain a very low value. (C) 2008 Elsevier Ltd. All rights reserved.

Photoluminescence of MEH-PPV with ultraviolet excitation

The basic optical properties of PPV-based polymers have been extensively studied due to their potential technological applications. However, a detailed investigation of electronic processes following photoexcitation in the ultraviolet is still lacking. We report photoluminescence measurements on poly(1-methoxy-4-ethylhexyloxy-paraphenylenevinylene) - MEH-PPV in the 2.0-5.6 eV range, with excitation up to 5.6 eV. The photoluminescence spectra lineshape is independent of excitation energy. The photoluminescence efficiency is high for energies well below the absorption maximum due to near-resonant excitation of the longest conjugated segments which are responsible for the PL It decreases strongly for excitation energies in the range 2.1-2.5 eV (up to the absorption maximum) and slightly from 2.5 to 5.6 eV. The results indicate that states excited in the ultraviolet rapidly relax nonradiatively to the lowest state, from where the usual luminescence occurs. (C) 2010 Elsevier B.V. All rights reserved.

Influence of chromium concentration on the optical-electronic properties of ruby microstructures

Films of amorphous aluminium nitride (AlN) were prepared by conventional radio frequency sputtering of an Al + Cr target in a plasma of pure nitrogen. The Cr-to-Al relative area determines the Cr content, which remained in the similar to 0-3.5 at% concentration range in this study. Film deposition was followed by thermal annealing of the samples up to 1050 degrees C in an atmosphere of oxygen and by spectroscopic characterization through energy dispersive x-ray spectrometry, photoluminescence and optical transmission measurements. According to the experimental results, the optical-electronic properties of the Cr-containing AlN films are highly influenced by both the Cr concentration and the temperature of the thermal treatments. In fact, thermal annealing at 1050 degrees C induces the development of structures that, because of their typical size and distinctive spectral characteristics, were designated by ruby microstructures (RbMSs). These RbMSs are surrounded by a N-rich environment in which Cr(3+) ions exhibit luminescent features not present in other Cr(3+)-containing systems such as ruby, emerald or alexandrite. The light emissions shown by the RbMSs and surroundings were investigated according to the Cr concentration and temperature of measurement, allowing the identification of several Cr(3+)-related luminescent lines. The main characteristics of these luminescent lines and corresponding excitation-recombination processes are presented and discussed in view of a detailed spectroscopic analysis.

Structural and spectroscopic properties of the diazocarbene radical (CNN) and its ions CNN(+) and CNN(-): a high-level theoretical investigation

The diazocarbene radical, CNN, and the ions CNN(+) and CNN(-) were investigated at a high level of theory. Very accurate structural parameters for the states X(3)Sigma(-) and A(3)Pi of CNN, and X(2)Pi of both CNN(+) and CNN(-) were obtained with the UCCSD(T) method using correlated-consistent basis functions with extrapolations to the complete basis set limit, with valence only and also with all electrons correlated. Harmonic and anharmonic frequencies were obtained for all species and the Renner parameter and average frequencies evaluated for the Pi states. At the UCCSD(T)/CBS(T-5) level of theory, Delta(f)H(0 K) = 138.89 kcal/mol and Delta(f)H(298 K) = 139.65 kcal/mol were obtained for diazocarbene; for the ionization potential and the electron affinity of CNN, 10.969 eV (252.95 kcal/mol), and 1.743 eV (40.19 kcal/mol), respectively, are predicted. Geometry optimization was also carried out with the CASSCF/MRCI/CBS(T-5) approach for the states X(3)Sigma(-) A(3)Pi, and a(1)Delta of CNN, and with the CASSCF/MRSDCI/aug-cc-pVTZ approach for the states b(1)Sigma(+), c(1)Pi, d(1)Sigma(-), and B(3)Sigma(-), and excitation energies (T(e)) evaluated. Vertical energies were calculated for 15 electronic states, thus improving on the accuracy of the five transitions already described, and allowing for a reliable overview of a manifold of other states, which is expected to guide future spectroscopic experiments. This study corroborates the experimental assignment for the vertical transition X (3)Sigma(-) <- E (3)Pi.

Resonant excitation of Mn local vibrational modes in the higher order Raman spectra of nanocrystalline Ga(1-x)Mn(x)N films

The effect of manganese on the vibrational properties of Ga(1-x)Mn(x)N (0 <= x <= 0.18) films has been investigated by Raman scattering using 488.0 and 632.8 nm photon excitations. The first-order transverse and longitudinal optical GaN vibrational bands were observed in the whole composition range using both excitations, while the corresponding overtones, as well as a prominent peak located in 1238 cm(-1) (153.5 meV) were only observed in the Mn-containing films under 488.0 nm excitation. We propose that the peak observed at 1238 cm(-1) is due to resonant Mn local vibrational modes, the excitation process being related to electronic transitions involving the Mn acceptor band.

Magnetic response and critical current properties of mesoscopic-size YBCO superconducting samples

In this contribution superconducting specimens of YBa(2)Cu(3)O(7-delta) were synthesized by a modified polymeric precursor method, yielding a ceramic powder with particles of mesoscopic-size. Samples of this powder were then pressed into pellets and sintered under different conditions. The critical current density was analyzed by isothermal AC-susceptibility measurements as a function of the excitation field, as well as with isothermal DC-magnetization runs at different values of the applied field. Relevant features of the magnetic response could be associated to the microstructure of the specimens and, in particular, to the superconducting intra- and intergranular critical current properties.

Coherent properties and Rabi oscillations in two-level donor systems

Coherent properties and Rabi oscillations in two-level donor systems, under terahertz excitation, are theoretically investigated. Here we are concerned with donor states in bulk GaAs and GaAs-(Ga,Al)As quantum dots. We study confinement effects, in the presence of an applied magnetic field, on the electronic and on-center donor states in GaAs- (Ga,Al)As dots, as compared to the situation in bulk GaAs, and estimate some of the associated decay rate parameters. Using the optical Bloch equations with damping, we study the time evolution of the Is and 2p(+) states in the presence of an applied magnetic field and of a terahertz laser. We also discuss the role played by the distinct dephasing rates on the photocurrent and calculate the electric dipole transition moment. Results indicate that the Rabi oscillations are more robust as the total dephasing rate diminishes, corresponding to a favorable coherence time.

Optical and electrical properties of polymerizing plasmas and their correlation with DLC film properties

Diamond-like carbon (DLC) films were grown from radiofrequency plasmas of acetylene-argon mixtures, at different excitation powers, P. The effects of this parameter on the plasma potential, electron density, electron temperature, and plasma activity were investigated using a Langmuir probe. The mean electron temperature increased from about 0.5 to about 7.0 eV while the mean electron density decreased from about 1.2x10(9) to about 0.2x10(9) cm(-3) as P was increased from 25 to 150 W. Both the plasma potential and the plasma activity were found to increase with increasing P. Through actinometric optical emission spectrometry, the relative concentrations of CH, [CH], and H, [H], in the discharge were mapped as a function of the applied power. A rise in [H] and a fall in [CH] with increasing P were observed and are discussed in relation to the plasma characteristics and the subimplantation model. The optical properties of the films were calculated from ultraviolet-visible spectroscopic data; the surface resistivity was measured by the two-point probe method. The optical gap, E(G), and the surface resistivity, rho(s), fall with increasing P. E(G) and rho(s) are in the ranges of about 2.0-1.3 eV and 10(14)-10(16) Omega/square, respectively. The plasma power also influences the film self-bias, V(b), via a linear dependence, and the effect of V(b) on ion bombardment during growth is addressed together with variation in the relative densities of sp(2) and sp(3) bonds in the films as determined by Raman spectroscopy.

Effect of Ultrasonic Excitation on the Porosity of Glass Ionomer Cement: A Scanning Electron Microscope Evaluation

Background: Ultrasonic excitation (US) was applied to glass ionomer cement (GIC) during early set time to increase the advantageous properties of this material. Purpose: The aim of this in vitro study was to assess the inner porosity of GIC after US. Study design: A total of 16 specimens, for each material, were prepared from high-viscosity GIC Fuji IX GP, Ketac Molar, and Ketac Molar Easymix. Half of these specimens (n = 8) received 30 s of US during the initial cement setting. After completion of the material setting, specimens were fractured and observed by scanning electronic microscopy to quantitatively assay porosity inside the material using Image J software. Results: Statistical data analysis revealed that US reduced the porosity for all tested materials (P <= 0.05). The following reductions (expressed in percentages) were achieved: Fuji IX-from 3.9% to 2.8%; Ketac Molar Easy Mix-from 4.4% to 2.6%, and Ketac Molar-from 2.4% to 1.6%. Conclusion: Under the tested conditions, US was an effective method for porosity reduction inside the material. Microsc. Res. Tech. 74:54-57, 2011. (C) 2010 Wiley-Liss, Inc.