135 resultados para Hückel-Möbius transition states
Resumo:
The complexes [Fe([9]aneN(2)S)(2)][ClO4](2), [Fe([9]aneN(2)S)(2)][ClO4](3) and [Fe([9]aneNS(2))(2)][ClO4](2) ([9]aneN(2)S = 1-thia-4. 7-diazacyclononane and [9]aneNS(2) = 1,4-dithia-7-azacyclononane) have been prepared and the latter two characterised by X-ray crystallography. The Mossbauer spectra (isomer shift/mm s(-1), quadrupole splitting/mm s(-1), 4.2 K) for [Fe([9]aneN(2)S)(2)][ClO4](2) (0.52, 0.57), [Fe([9]aneN(2)S)(2)][ClO4](3) (0.25, 2.72) and [Fe([9]aneNS(2))(2)][ClO4](2) (0.43, 0.28) are typical for iron(II) and iron(III) complexes. Variable-temperature susceptibility measurements for [Fe([9]aneN(2)S)(2)][ClO4](2) (2-300 K) revealed temperature-dependent behaviour in both the solid state [2.95 mu(B) (300 K)-0.5 mu(B) (4.2 K)] and solution (Delta H degrees 20-22 kJ mol(-1), Delta S degrees 53-60 J mol(-1) K-1). For [Fe([9]aneN(2)S)(2)][ClO4](3) in the solid state [2.3 mu(B) (300 K)-1.9 mu(B) (4.2 K)] the magnetic data were fit to a simple model (H = -lambda L . S + mu L-z) to give the spin-orbit coupling constant (lambda) of -260 +/- 10 cm(-1). The solid-state X-band EPR spectrum of [Fe([9]aneN(2)S)(2)][ClO4](3) revealed axial symmetry (g(perpendicular to) = 2.607, g(parallel to) = 1.599). Resolution of g(perpendicular to) into two components at Q-band frequencies indicated a rhombic distortion. The low-temperature single-crystal absorption spectra of [Fe([9]aneN(2)S)(2)][ClO4](2) and [Fe([9]aneNS(2))(2)][ClO4](2) exhibited additional bands which resembled pseudotetragonal low-symmetry splitting of the parent octahedral (1)A(1g) --> T-1(2g) and (1)A(1g) ---> T-1(1g) transitions. However, the magnitude of these splittings was too large, requiring 10Dq for the thioether donors to be significantly larger than for the amine donors. Instead, these bands were tentatively assigned to weak, low-energy S --> Fe-II charge-transfer transitions. Above 200 K, thermal occupation of the high-spin T-5(2g) ground state resulted in observation of the T-5(2g) --> E-5(g) transition in the crystal spectrum of [Fe([9]aneN(2)S)(2)][ClO4](2). From a temperature-dependence study, the separation of the low-spin (1)A(1g) and high-spin T-5(2g) ground states was approximately 1700 cm(-1). The spectrum of the iron(III) complex [Fe([9]aneN(2)S)(2)][ClO4](3) is consistent with a low-spin d(5) configuration.
Resumo:
We study the interaction of a two-level atom with two lasers of different frequencies and amplitudes: a strong laser of Rabi frequency 2 Ohm(1) on resonance with the atomic transition, and a weaker laser detuned by subharmonics (2 Ohm(1)/n) of the Rabi frequency of the first. We find that under these conditions the second laser couples the dressed states created by the first in an n-photon process, resulting in doubly dressed states and in a ''multiphoton ac Stark'' effect. We calculate the eigenstates of the doubly dressed atom and their energies, and illustrate the role of this multiphoton ac Stark effect in its fluorescence, absorption, and Autler-Townes spectra. [S1050-2947(98)07607-0].
Resumo:
We present some exact results for the effect of disorder on the critical properties of an anisotropic XY spin chain in a transverse held. The continuum limit of the corresponding fermion model is taken and in various cases results in a Dirac equation with a random mass. Exact analytic techniques can then be used to evaluate the density of states and the localization length. In the presence of disorder the ferromagnetic-paramagnetic or Ising transition of the model is in the same universality class as the random transverse field Ising model solved by Fisher using a real-space renormalization-group decimation technique (RSRGDT). If there is only randomness in the anisotropy of the magnetic exchange then the anisotropy transition (from a ferromagnet in the x direction to a ferromagnet in the y direction) is also in this universality class. However, if there is randomness in the isotropic part of the exchange or in the transverse held then in a nonzero transverse field the anisotropy transition is destroyed by the disorder. We show that in the Griffiths' phase near the Ising transition that the ground-state energy has an essential singularity. The results obtained for the dynamical critical exponent, typical correlation length, and for the temperature dependence of the specific heat near the Ising transition agree with the results of the RSRODT and numerical work. [S0163-1829(99)07125-8].
Resumo:
The general-care glass ceiling hypothesis states that not only is it more difficult for women than for men to be promoted up levels of authority hierarchies within workplaces but also that the obstacles women face relative to men become greater as they move rtp the hierarchy. Gender-based discrimination in promotions is not simply present across levels of hierarchy but is more intense at higher levels. Empirically, this implies that the relative rates of women being promoted to higher levels compared to men should decline with the level of the hierarchy. This article explores this hypothesis with data from three countries: the United States, Australia, and Sweden. The basic conclusion is that while there is strong evidence for a general gender gap in authority-the odds of women having authority are less than those of men-there is no evidence for systematic glass ceiling effects in the United States and only weak evidence for such effects in the other two countries.
Resumo:
A two-step method of loading controlled amounts of transition metal cations into alumina pillared clays (Al-PILCs) is proposed. First, calcined Al-PILC was dispersed into an aqueous solution of sodium or ammonium ions. Increasing the pH of the dispersion resulted in an increase in the amount of cations loaded into the clay. The ion-doped Al-PILC was then exchanged with an aqueous solution of transition metal salt at a pH of similar to 4.5 to replace Na+ or NH4+ ions by transition metal cations. Analytical techniques such as atomic absorption spectroscopy, X-ray diffraction, diffuse reflectance-ultraviolet-visible spectroscopy, as well as N-2 adsorption were used to characterize the PILC products with and without the loading of metal ions. The introduced transition metal species exist in the forms of hydrated ions in the PILC hosts. The content of transition metal ions in the final product increased with the amount of Na+ or NH4+ loaded in the first step so that by controlling the pH of the dispersion in the first step, one can control the doping amounts of transition metal cations into Al-PILCs. A sample containing 0.125 mmol/g of nickel was thus obtained, which is similar to 3 times of that obtained by directly exchanging Al-PILC with Ni(NO3)(2) solution, while the pillared layered structures of the Al-PILC remained. The porosity analysis using N-2 adsorption data indicated that most of the doped transition metal ions dispersed homogeneously in the micropores of the Al-PILC, significantly affecting the micropore structure.
Resumo:
Sensory axons of different sensory modalities project into typical domains within insect ganglia. Tactile and gustatory axons project into a ventral layer of neuropil and proprioceptive afferents, including chordotonal axone, into an intermediate or dorsal layer. Here, we describe the central projections of sensory neurons in the first instar Drosophila larva, relating them to the projection of the same sensory afferents in the embryo and to sensory afferents of similar type in other insects. Several neurons show marked morphologic changes in their axon terminals in the transition between the embryo and larva. During a short morphogenetic period late in embryogenesis, the axon terminals of the dorsal bipolar dendrite stretch receptor change their shape and their distribution within the neuromere. In the larva, external sense organ neurons (es) project their axons into a ventral layer of neuropil. Chordotonal sensory neurons (ch) project into a slightly more dorsal region that is comparable to their projection in adults. The multiple dendrite (md) neurons show two distinctive classes of projection. One group of md neurons projects into the ventral-most neuropil region, the same region into which es neurons project. Members of this group are related by lineage to es neurons or share a requirement for expression of the same proneural gene during development. Other md neurons project into a more dorsal region. Sensory receptors projecting into dorsal neuropil possibly provide proprioceptive feedback from the periphery to central motorneurons and are candidates for future genetic and cellular analysis of simple neural circuitry. J. Comp. Neurol. 425:34-44, 2000. (C) 2000 Wiley-Liss, Inc.
Resumo:
OBJECTIVE: To describe variation in all cause and selected cause-specific mortality rates across Australia. METHODS: Mortality and population data for 1997 were obtained from the Australian Bureau of Statistics. All cause and selected cause-specific mortality rates were calculated and directly standardised to the 1997 Australian population in 5-year age groups. Selected major causes of death included cancer, coronary artery disease, cerebrovascular disease, diabetes, accidents and suicide. Rates are reported by statistical division, and State and Territory. RESULTS: All cause age-standardised mortality was 6.98 per 1000 in 1997 and this varied 2-fold from a low in the statistical division of Pilbara, Western Australia (5.78, 95% confidence interval 5.06-6.56), to a high in Northern Territory-excluding Darwin (11.30, 10.67-11.98). Similar mortality variation (all p<0.0001) exists for cancer (1.01-2.23 per 1000) and coronary artery disease (0.99-2.23 per 1000), the two biggest killers. Larger variation (all p<0.0001) exists for cerebrovascular disease (0.7-11.8 per 10,000), diabetes (0.7-6.9 per 10,000), accidents (1.7-7.2 per 10,000) and suicide (0.6-3.8 per 10,000). Less marked variation was observed when analysed by State and Territory. but Northern Territory consistently has the highest age-standardised mortality rates. CONCLUSIONS: Analysed by statistical division, substantial mortality gradients exist across Australia, suggesting an inequitable distribution of the determinants of health. Further research is required to better understand this heterogeneity.
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We analyze the fidelity of teleportation protocols, as a function of resource entanglement, for three kinds of two-mode oscillator states: states with fixed total photon number, number states entangled at a beam splitter, and the two-mode squeezed vacuum state. We define corresponding teleportation protocols for each case including phase noise to model degraded entanglement of each resource.
Resumo:
We investigate the utility of nonclassical states of simple harmonic oscillators, particularly a superposition of coherent states, for sensitive force detection. We find that like squeezed states, a superposition of coherent states allows displacement measurements at the Heisenberg limit. Entangling many superpositions of coherent states offers a significant advantage over a single-mode superposition state with the same mean photon number.
Resumo:
Electron spin transient nutation (ESTN) experiments show that the spin multiplicity of the ground state of C-60(3-) in frozen solution is a doublet with S = 1/2. In purified samples, there is no evidence for excited states or other species with higher multiplicity. In the anions Of C120On- (n = 2, 3, 4), where the CW EPR experiments have shown that a mixture of species is present, ESTN experiments confirm that a doublet with S = 1/2 is associated with the 3- anion and triplets with S = 1 are associated with the 2- and 4- anions. A weak nutation peak attributable to m(s) = -1/2 1/2 transitions within a quartet state may arise from association of anions with spins of 1/2 and 1 in solute aggregates.
Resumo:
Teen Triple P is a multilevel system of intervention that is designed to provide parents with specific strategies to promote the positive development of their teenage children as they make the transition into high school and through puberty. The program is based on a combination of education about the developmental needs of adolescents, skills training to improve communication and problem-solving, plus specific modules to deal with common problems encountered by parents and adolescents that can escalate into major conflict and violence. It is designed to increase the engagement of parents of adolescent and pre-adolescent children by providing them with easy access to evidencebased parenting advice and support. This paper presents data collected as part of a survey of over 1400 students in first year high school at 9 Brisbane schools. The survey instrument was constructed to obtain students' reports about behaviour which is known to be associated with their health and wellbeing, and also on the extent to which their parents promoted or discouraged such behaviour at home, at school, and in their social and recreational activities in the wider community. Selected data from the survey were extracted and presented to parents at a series of parenting seminars held at the schools to promote appropriate parenting of teenagers. The objectives were to provide parents with accurate data about teenagers' behaviour, and about teenagers' reports of how they perceived their parents' behaviour. Normative data on parent and teenager behaviour will be presented from the survey as well as psychometric data relating to the reliability and validity of this new measure. Implications of this strategy for increasing parent engagement in parenting programs that aim to reduce behavioural and emotional problems in adolescents will be discussed.
Resumo:
A Cellular-Automaton Finite-Volume-Method (CAFVM) algorithm has been developed, coupling with macroscopic model for heat transfer calculation and microscopic models for nucleation and growth. The solution equations have been solved to determine the time-dependent constitutional undercooling and interface retardation during solidification. The constitutional undercooling is then coupled into the CAFVM algorithm to investigate both the effects of thermal and constitutional undercooling on columnar growth and crystal selection in the columnar zone, and formation of equiaxed crystals in the bulk liquid. The model cannot only simulate microstructures of alloys but also investigates nucleation mechanisms and growth kinetics of alloys solidified with various solute concentrations and solidification morphologies.