Dependence of crystal field splitting of 5d levels on hosts in the halide crystals

The crystal field splitting of 5d level of EU2+ and Ce3+ in halide crystals has been studied. Our results indicate that the 10Dq splitting can be directly related to the homopolar part of average energy gap, the coordination number of central (doped) ion, the charge of neighboring anions and bond ionicity between central ion to nearest anions. A relation between the 10Dq splitting and the above mentioned factors is presented. Our calculated results are in reasonable agreement with diverse experiments.

Effect of configuration and conformation on the spin multiplicity in xylylene type biradicals

The singlet-triplet splitting energy gap DeltaE(S.T) = E-S - E-T is calculated for the ortho-, meta-, and para-xylylenes and their heteroatomic analogous by means of AM1-CI approach. It is shown that when the radical centers R-.(R-.=H2C.-,H2N.+- or HN.-) are twisted sufficiently Tar out of conjugation with the benzene ring, DeltaE(S.T) tends to zero or is negative, i.e, ortho-, meta-, and para-phenylenes turn into weak ferromagnetic or antiferromagnetic coupling unit, while they are strong ferromagnetic (meta-isomers) or antiferromagnetic (ortho-, para-isomers) coupling units under planar conformation. It is suggested that serious twisted conformation is not recommended candidate for the design of novel high-spin molecules with stable high-spin ground states by ortho- or para-phenylene coupling unit.

Luminescent properties of divalent samarium-doped strontium hexaborate

The valence change of samarium from trivalent to divalent in strontium hexaborate (SrB6O10) prepared in air is observed. The temperature dependence of the luminescence and vibronic transitions of Sm2+ are studied. The Sm2+ ions occupy three crystallographic sites. With increasing temperature, the D-5(0)-->F-7(0) transition line exhibits red shifts, and the half-width increases. At room temperature, due to the thermal population through the 4f(5)5d channel, the D-5(1)-->F-7(J) transitions are observed even though the vibrational energy is very close to the energy gap between the D-5(1) and D-5(0) levels in the host. A coupled phonon energy of about 108 cm(-1) is determined from the vibronic transitions of Sm2+ in the host.

The effect of some triazole derivatives as inhibitors for the corrosion of mild steel in 1 M hydrochloric acid

Corrosion inhibition by some new triazole derivatives on mild steel in 1 M hydrochloric acid solutions has been investigated by weight loss test, electrochemical measurement, scanning electronic microscope analysis and quantum chemical calculations. The results indicate that these compounds act as mixed-type inhibitors retarding the anodic and cathodic corrosion reactions and do not change the mechanism of either hydrogen evolution reaction or mild steel dissolution. The studied compounds following the Langmuir adsorption isotherm, and the thermodynamic parameters were determined and discussed. The effect of molecular structure on the inhibition efficiency has been investigated by ab initio quantum chemical calculations. The electronic properties such as highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) energy levels, energy gap (LUMO-HOMO), dipole moment and molecular orbital densities were calculated. (C) 2009 Published by Elsevier B.V.

2,3,5-triphenyl-2H-tetrazolium chloride and 2,4,6-tri(2-pyridyl)-s-triazine on the corrosion of mild steel in HCl

Electrochemical measurement, quantum chemical method, and scanning electron microscopy (SEM) were performed to investigate the inhibitive effect of 2,3,5-triphenyl-2H-tetrazolium chloride (TTC) and 2,4,6-tri(2-pyridyl)-s-triazine(TPT) on the corrosion of mild steel in 1mol.L-1 HCl at room temperature. Impedance spectroscopy measurement showed that the polarization resistance increased and that double layer capacitance decreased with the increase in the inhibitive concentration, and the results of potentiodynamic polarization showed that the inhibitors suppressed both cathodic and anodic processes of steel corrosion without change in the mechanism. Higher the orbital density distribution strength of the lowest unoccupied molecular orbital, higher is the molecule dipole, and lower energy gap between the energy of the highest occupied molecular orbital and the energy of the lowest unoccupied molecular orbital resulted in higher inhibitory efficiency. The results of SEM analysis showed that the metal was protected from aggressive corrosion by the addition of TTC and TPT.

Experimental and theoretical investigation of the adsorption behaviour of new triazole derivatives as inhibitors for mild steel corrosion in acid media

Three triazole derivatives (4-chloro-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (CATM), 4-methoxyl-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (MATM) and 4-fluoro-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (FATM)) have been synthesized as new inhibitors for the corrosion of mild steel in acid media. The inhibition efficiencies of these inhibitors were evaluated by means of weight loss and electrochemical techniques such as electrochemical impedance spectroscopy (EIS) and polarization curves. Then the surface morphology was studied by scanning electron microscopy (SEM). The adsorption of triazole derivatives is found to obey Langmuir adsorption isotherm, and the thermodynamic parameters were determined and discussed. The relationship between molecular structure of these compounds and their inhibition efficiency has been investigated by ab initio quantum chemical calculations. The electronic properties such as the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO) energy levels, energy gap (LUMO-HOMO), dipole moment and molecular orbital densities were computed. (c) 2007 Elsevier Ltd. All rights reserved.

Phase-resolved emission spectroscopy of a hydrogen rf discharge for the determination of quenching coefficients

Collisional effects can have strong influences on the population densities of excited states in gas discharges at elevated pressure. The knowledge of the pertinent collisional coefficient describing the depopulation of a specific level (quenching coefficient) is, therefore, important for plasma diagnostics and simulations. Phase resolved optical emission spectroscopy (PROES) applied to a capacitively coupled rf discharge excited with a frequency of 13.56 MHz in hydrogen allows the measurement of quenching coefficients for emitting states of various species, particularly of noble gases, with molecular hydrogen as a collision partner. Quenching coefficients can be determined subsequent to electron-impact excitation during the short field reversal phase within the sheath region from the time behavior of the fluorescence. The PROES technique based on electron-impact excitation is not limited â?? in contrast to laser techniques â?? by optical selection rules and the energy gap between the ground state and the upper level of the observed transition. Measurements of quenching coefficients and natural fluorescence lifetimes are presented for several helium (3 1S,4 1S,3 3S,3 3P,4 3S), neon (2p1 ,2p2 ,2p4 ,2p6), argon (3d2 ,3d4 ,3d18 and 3d3), and krypton (2p1 ,2p5) states as well as for some states of the triplet system of molecular hydrogen.

Determination of quenching coefficients in a hydrogen RF discharge by time-resolved optical emission spectroscopy

In gas discharges at elevated pressure, radiation-less collisional de-excitation (quenching) has a strong influence on the population of excited states. The knowledge of quenching coefficients is therefore important for plasma diagnostics and simulations. A novel time-resolved optical emission spectroscopic (OES) technique allows the measurement of quenching coefficients for emission lines of various species, particularly of noble gases, with molecular hydrogen as collision partner. The technique exploits the short electron impact excitation during the field reversal phase within the sheath region of a hydrogen capacitively coupled RF discharge at 13.56 MHz. Quenching coefficients can be determined subsequent to this excitation from the effective lifetime of the fluorescence decay at various hydrogen pressures. The measured quenching coefficients agree very well with results obtained by means of laser excitation. The time-resolved OES technique based on electron impact excitation is not limited - in contrast to laser techniques - by optical selection rules and the energy gap between the ground state and the observed excited level.

Insight into the adsorption competition and the relationship between dissociation and association reactions in ammonia synthesis

Ammonia synthesis on three metal surfaces (Zr, Ru, and Pd) is investigated using density functional theory calculations. In addition to N-2 dissociation, all the transition states of the hydrogenation reactions from N to NH3 are located and the reaction energy profiles at both low and high surface coverages are compared and analyzed. The following are found: (i) Surface coverage effect on dissociation reactions is more significant than that on association reactions. (ii) The difference between N and H chemisorption energies, the so-called chemisorption energy gap which is a measure of adsorption competition, is vital to the reactivity of the catalysts. (iii) The hydrogenation barriers can considerably affect the overall rate of ammonia synthesis. A simple model to describe the relationship between dissociation and association reactions is proposed. (c) 2007 American Institute of Physics.

Gapped Two-Body Hamiltonian for Continuous-Variable Quantum Computation

We introduce a family of Hamiltonian systems for measurement-based quantum computation with continuous variables. The Hamiltonians (i) are quadratic, and therefore two body, (ii) are of short range, (iii) are frustration-free, and (iv) possess a constant energy gap proportional to the squared inverse of the squeezing. Their ground states are the celebrated Gaussian graph states, which are universal resources for quantum computation in the limit of infinite squeezing. These Hamiltonians constitute the basic ingredient for the adiabatic preparation of graph states and thus open new venues for the physical realization of continuous-variable quantum computing beyond the standard optical approaches. We characterize the correlations in these systems at thermal equilibrium. In particular, we prove that the correlations across any multipartition are contained exactly in its boundary, automatically yielding a correlation area law. © 2011 American Physical Society.

A multiconfigurational time-dependent Hartree-Fock method for excited electronic states. II. Coulomb interaction effects in single conjugated polymer chains

Conjugated polymers have attracted considerable attention in the last few decades due to their potential for optoelectronic applications. A key step that needs optimisation is charge carrier separation following photoexcitation. To understand better the dynamics of the exciton prior to charge separation, we have performed simulations of the formation and dynamics of localised excitations in single conjugated polymer strands. We use a nonadiabatic molecular dynamics method which allows for the coupled evolution of the nuclear degrees of freedom and of multiconfigurational electronic wavefunctions. We show the relaxation of electron-hole pairs to form excitons and oppositely charged polaron pairs and discuss the modifications to the relaxation process predicted by the inclusion of the Coulomb interaction between the carriers. The issue of charge photogeneration in conjugated polymers in dilute solution is also addressed. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3600404]

Temperature dependence of the mid-infrared dielectric function of YBCO in the ab plane

We have excited mid-infrared surface plasmons in two YBCO thin films of contrasting properties using attenuated total reflection of light and found that the imaginary part of the dielectric function decreases linearly with reduction in temperature. This result is in contrast with the commonly reported conclusion of infrared normal reflectance studies. If sustained it may clarify the problem of understanding the normal state properties of YBCO and the other cuprates. The dielectric function of the films, epsilon = epsilon(1) + i epsilon(2), was determined between room temperature and 80K: epsilon(1) was found to be only slightly temperature dependent but somewhat sample dependent, probably as a result of surface and grain boundary contamination. The imaginary part, epsilon(2), (and the real part of the conductivity, sigma(1),) decreased linearly with reduction in temperature in both films. Results obtained were: for film 1: epsilon(1) = - 14.05 - 0.0024T and epsilon(2) - 4.11 + 0.086T and for film 2: epsilon(1) = - 24.09 + 0.0013T and epsilon(2) = 7.66 + 0.067T where T is the temperature in Kelvin. An understanding of the results is offered in terms of temperature-dependent intrinsic intragrain inelastic scattering and temperature-independent contributions: elastic and inelastic grain boundary scattering and optical interband (or localised charge) absorption. The relative contribution of each is estimated. A key conclusion is that the interband (or localised charge) absorption is only similar to 10%. Most importantly, the intrinsic scattering rate, 1/tau, decreases linearly with fall in temperature, T, in a regime where current theory predicts dependence on frequency, omega, to dominate. The coupling constant, lambda, between the charge carriers and the thermal excitations has a value of 1.7, some fivefold greater than the far infrared value. These results imply a need to restate the phenomenology of the normal state of high temperature superconductors and seek a corresponding theoretical understanding.

Far infrared reflectance and optical properties of organic superconductor (TMTSF)2ClO4 /

Polarized reflectance measurements of the quasi I-D charge-transfer salt (TMTSFh CI04 were carried out using a Martin-Puplett-type polarizing interferometer and a 3He refrigerator cryostat, at several temperatures between 0.45 K and 26 K, in the far infrared, in the 10 to 70 cm- 1 frequency range. Bis-tetramethyl-tetraselena-fulvalene perchlorate crystals, grown electrochemically and supplied by K. Behnia, of dimensions 2 to 4 by 0.4 by 0.2 mm, were assembled on a flat surface to form a mosaic of 1.5 by 3 mm. The needle shaped crystals were positioned parallel to each other along their long axis, which is the stacking direction of the planar TMTSF cations, exposing the ab plane face (parallel to which the sheets of CI04 anions are positioned). Reflectance measurements were performed with radiation polarized along the stacking direction in the sample. Measurements were carried out following either a fast (15-20 K per minute) or slow (0.1 K per minute) cooling of the sample. Slow cooling permits the anions to order near 24 K, and the sample is expected to be superconducting below 1.2 K, while fast cooling yields an insulating state at low temperatures. Upon the slow cooling the reflectance shows dependence with temperature and exhibits the 28 cm- 1 feature reported previously [1]. Thermoreflectance for both the 'slow' and 'fast' cooling of the sample calculated relative to the 26 K reflectance data indicates that the reflectance is temperature dependent, for the slow cooling case only. A low frequency edge in the absolute reflectance is assigned an electronic origin given its strong temperature dependence in the relaxed state. We attribute the peak in the absolute reflectance near 30 cm-1 to a phonon coupled to the electronic background. Both the low frequency edge and the 30 cm-1 feature are noted te shift towards higher frequcncy, upon cntering the superconducting state, by an amount of the order of the expected superconducting energy gap. Kramers-Kronig analysis was carried out to determine the optical conductivity for the slowly cooled sample from the measured reflectance. In order to do so the low frequency data was extrapolated to zero frequency using a Hagen-Ru bens behaviour, and the high frequency data was extended with the data of Cao et al. [2], and Kikuchi et al. [3]. The real part of the optical conductivity exhibits an asymmetric peak at 35 cm-1, and its background at lower frequencies seems to be losing spectral weight with lowering of the temperature, leading us to presume that a narrow peak is forming at even lower frequencies.

Optical properties of organic superconductor K-(BETS)2FeBr4 /

K-(BETS)2FeBr4 is a quasi-2D charge transfer organic metal with interesting electronic and magnetic properties. It undergoes a transition to an antiferromagnetic (AF) state at ambient pressure at the Neel temperature (T^^) = 2.5 K, as well as to a superconducting (SC) state at 1.1 K [1]. The temperature dependence of the electrical resistivity shows a small decrease at T;v indicating the resistivity drops as a result of the onset of the ordering of Fe'*''" spins. A sharp drop in the resistivity at 1.1 K is due to its superconducting transition. The temperature dependence of the susceptibility indicates an antiferromagnetic spin structure with the easy axis parallel to the a-axis. The specific heat at zero-field shows a large peak at about 2.4 K, which corresponds to the antiferromagnetic transition temperature (Tat) and no anomaly is observed around the superconducting transition temperature (1.1 K) demonstrating that the magnetically ordered state is not destroyed by the appearance of another phase transition (the superconducting transition) in the 7r-electron layers [1], [2]. This work presents an investigation of how the low frequency electromagnetic response is affected by the antiferromagnetic and superconducting states, as well as the onset of strong correlation. The location of the easy axis of three samples was determined and polarized thermal reflectance measurements of these «-(BETS)2FeBr4 samples oriented with their vertical axis along the a- and c axes were then carried out using a *He refrigerator cryostat and a Martin-Puplett type polarizing interferometer at various temperatures (T = 0.5 K, 1.4 K. 1.9 K, 2.8 K) above and below the superconducting state and/or antiferromagnetic state. Comparison of the SC state to the normal state along the o- and c-axes indicates a rising thermal reflectance at low frequencies (below 10 cm"' ) which may be a manifestation of the superconducting energy gap. A dip-Hke feature is detected at low frequencies (below 15 cm"') in the thermal reflectance plots which probe the antiferromagnetic state along the two axes, and may be due to the opening of a gap in the excitation spectrum as a result of the antiferromagnetism. In another set of experiments, thermal reflectance measurements carried out along the a- and c-axes at higher temperatures (10 K-80 K) show that the reflectivity decreases with increasing temperature to 60 K (the coherence temperature) above which it increases again. Comparison of the thermal reflectance plots along the a- and c-axes at higher temperatures reveals an anisotropy between these two axes. The Hagen-Rubens thermal reflectance plots corresponding to an average over the ac-plane were calculated using experimental hterature resistivity values. Comparison of the Hagen-Rubens plots with the experimental thermal reflectance along the a- and c-axes indicates that both exhibit the general trend of a decrease in thermal reflectance with increasing frequency, however the calculated Hagen-Rubens thermal reflectance at different temperatures is much lower than the experimental curves.

Far infrared spectroscopy of heavy fermion superconductor CeCoIn5

The optical response to far infrared radiation has been measured on a mosaic of heavy fermion CeColnssingle crystals. The superconducting transition temperature of the crystals has been determined by van der Pauw resistivity and ac-susceptibility measurements as Tc = 2.3 K. The optical measurements were taken above and below the transition temperature using a 3He cryostat and step and integrate Martin-Puplett type polarizing interferometer. The absolute reflectance of the heavy fermion CeColns in the superconducting state in range (0, 100)cm-1 was calculated from the measured thermal reflectance, using the normal state data of Singley et al and a low frequency extrapolation for a metallic material in the Hagen-Rubens regime. By means of Kramers-Kronig analysis the absolute reflectance was used to calculate the optical conductivity of the sample. The real part of the calculated complex conductivity 0-(w) ofCeColns indicates a possible opening of an energy gap close to 50 em-I.