Evidence for energy relaxation via a radiative cascade in surface-passivated PbS quantum dots

Multiple emission peaks have been observed from surface passivated PbS nanocrystals displaying strong quantum confinement. The emission spectra are shown to be strongly dependent on the excited-state parity. We also find that intraband energy relaxation from initial states excited far above the band-edge is nearly three orders of magnitude slower than that found in other nanocrystal quantum dots, providing evidence of inefficient energy relaxation via phonon emission. The initial-state parity dependence of the photoluminescent emission properties suggests that energy relaxation from the higher excited states occurs via a radiative cascade, analogous to energy relaxation in atomic systems. Such radiative cascade emission is possible from ideal zero-dimensional semiconductors, where electronic transitions can be decoupled from phonon modes.

Identifying the energy gap: Magnitude and determinants of 5-year weight gain in midage women

Objective: The aims of this study were to estimate average yearly weight gain in midage women and to identify the determinants of weight gain and gaining weight at double the average rate. Research Methods and Procedures: The study sample comprised 8071 participants (45 to 55 years old) in the Australian Longitudinal Study on Women's Health who completed mailed surveys in 1996, 1998, and 2001. Results: On average, the women gained almost 0.5 kg per year [average 2.42 kg (95% confidence interval, 2.29 to 2.54) over 5 years]. In multivariate analyses, variables associated with energy balance (physical activity, sitting time, and energy intake), as well as quitting smoking, menopause/hysterectomy, and baseline BMI category were significantly associated with weight gain, but other behavioral and demographic characteristics were not. After adjustment for all of the other biological and behavioral variables, the odds of gaining weight at about twice the average rate (> 5 kg over 5 years) were highest for women who quit smoking (odds ratio = 2.94; 95% confidence interval, 2.17, 3.96). There were also independent relationships between the odds of gaining > 5 kg and lower levels of habitual physical activity, more time spent sitting, energy intake (but only in women with BMI > 25 at baseline), menopause transition, and hysterectomy. Discussion: The average weight gain equates with an energy imbalance of only about 10 kcal or 40 kJ per day, which suggests that small sustained changes in the modifiable behavioral variables could prevent further weight gain.

Energy profiles for ketene cyclizations. interconversion of 1,3-oxazin-6-ones, mesoionic 1,3-oxazinium olates and acylketenes, imidoylketenes, oxoketenimines, and cyclization products

The energy surface connecting oxazinium olates 9, several possible conformers of ketenes 10 and 11, and the final cyclization products 12, 13 and 14, as well as the isomeric 1,3-oxazine-6-ones 15, ring opening of the latter to N-acylimidoylketenes 16, and subsequent rearrangement of 16 to oxoketenimines 17, azetinones 18, and the cyclization products 19 and 20 are evaluated computationally at the B3LYP/6-31G* and B3LYP/6-311+G*//B3LYP/6-31G* levels. The cyclizations of ketenes to oxazinium olates 9 and oxazines 15 have the characteristics of pseudopericyclic reactions. Plots of the energy vs internal reaction coordinate for the cyclization of transoid acylketenes such as 10 to 9 (via TS1) and 16 to 15 (via TS7) feature two inflection points and indicate that the part of the energy surface above the lower inflection points describe internal rotation of the acyl function in the ketene moiety, and the part below this point describes the cyclization of the cisoid ketene to the planar mesoionic oxazinium olate 9 or oxazinone 15. The 1,3-shifts of the OR group that interconvert ketenes 16 and ketenimines 17 via four-membered cyclic transition states TS8 behave similarly, the first portion (from the ketenimine side) of the activation barrier being due largely to internal rotation of substituents, and the top part being due to the 1,3-shift proper.

Spin boson models for quantum decoherence of electronic excitations of biomolecules and quantum dots in a solvent

We give a theoretical treatment of the interaction of electronic excitations (excitions) in biomolecules and quantum dots with the surrounding polar solvent. Significant quantum decoherence occurs due to the interaction of the electric dipole moment of the solute with the fluctuating electric dipole moments of the individual molecules in the solvent. We introduce spin boson models which could be used to describe the effects. of decoherence on the quantum dynamics of biomolecules which undergo light-induced conformational change and on biomolecules or quantum dots which are coupled by Forster resonant energy transfer.

Theory of strongly correlated electron systems. I. Intersite coulomb interaction and the approximation of renormalized fermions in total energy calculations

The diagrammatic strong-coupling perturbation theory (SCPT) for correlated electron systems is developed for intersite Coulomb interaction and for a nonorthogonal basis set. The construction is based on iterations of exact closed equations for many - electron Green functions (GFs) for Hubbard operators in terms of functional derivatives with respect to external sources. The graphs, which do not contain the contributions from the fluctuations of the local population numbers of the ion states, play a special role: a one-to-one correspondence is found between the subset of such graphs for the many - electron GFs and the complete set of Feynman graphs of weak-coupling perturbation theory (WCPT) for single-electron GFs. This fact is used for formulation of the approximation of renormalized Fermions (ARF) in which the many-electron quasi-particles behave analogously to normal Fermions. Then, by analyzing: (a) Sham's equation, which connects the self-energy and the exchange- correlation potential in density functional theory (DFT); and (b) the Galitskii and Migdal expressions for the total energy, written within WCPT and within ARF SCPT, a way we suggest a method to improve the description of the systems with correlated electrons within the local density approximation (LDA) to DFT. The formulation, in terms of renormalized Fermions LIDA (RF LDA), is obtained by introducing the spectral weights of the many electron GFs into the definitions of the charge density, the overlap matrices, effective mixing and hopping matrix elements, into existing electronic structure codes, whereas the weights themselves have to be found from an additional set of equations. Compared with LDA+U and self-interaction correction (SIC) methods, RF LDA has the advantage of taking into account the transfer of spectral weights, and, when formulated in terms of GFs, also allows for consideration of excitations and nonzero temperature. Going beyond the ARF SCPT, as well as RF LIDA, and taking into account the fluctuations of ion population numbers would require writing completely new codes for ab initio calculations. The application of RF LDA for ab initio band structure calculations for rare earth metals is presented in part 11 of this study (this issue). (c) 2005 Wiley Periodicals, Inc.

Theory of strongly correlated electron systems. II. Including correlation effects into electronic structure calculations

We have previously shown that a division of the f-shell into two subsystems gives a better understanding of the cohesive properties as well the general behavior of lanthanide systems. In this article, we present numerical computations, using the suggested method. We show that the picture is consistent with most experimental data, e.g., the equilibrium volume and electronic structure in general. Compared with standard energy band calculations and calculations based on the self-interaction correction and LIDA + U, the f-(non-f)-mixing interaction is decreased by spectral weights of the many-body states of the f-ion. (c) 2005 Wiley Periodicals, Inc.

Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged Co-III-Fe-II complexes

The effects of pressure and temperature on the energy (E-op) of the metal-to-metal charge transfer (MMCT, Fe-II --> Co-III) transition of the cyano-bridged complexes trans - [(LCoNCFe)-Co-14(CN)(5)](-) and cis-[(LCoNCFe)-Co-14(CN)(5)](-) (where L-14 = 6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine) were examined. The changes in the redox potentials of the cobalt and iron metal centres with pressure and temperature were also examined and the results interpreted with Marcus Hush theory. The observed redox reaction volumes can mainly be accounted for in terms of localised electrostriction effects. The shifts in E-op due to both pressure and temperature were found to be less than the shifts in the energy difference (E degrees) between the Co-III-Fe-II and Co-II-Fe-III redox isomers. The pressure and temperature dependence of the reorganisational energy, as well as contributions arising from the different spin states of Co-II, are discussed in order to account for this trend. To study the effect of pressure on Co-III electronic absorption bands, a new cyano-bridged complex, trans - [(LCoNCCo)-Co-14(CN)(5)], was prepared and characterised spectroscopically and structurally. X-Ray crystallography revealed this complex to be isostructural with trans -[(LCoNCFe)-Co-14(CN)(5)] center dot 5H(2)O.

Self-consistent theory of atomic Fermi gases with a Feshbach resonance at the superfluid transition

A self-consistent theory is derived to describe the BCS-Bose-Einstein-condensate crossover for a strongly interacting Fermi gas with a Feshbach resonance. In the theory the fluctuation of the dressed molecules, consisting of both preformed Cooper pairs and bare Feshbach molecules, has been included within a self-consistent T-matrix approximation, beyond the Nozieres and Schmitt-Rink strategy considered by Ohashi and Griffin. The resulting self-consistent equations are solved numerically to investigate the normal-state properties of the crossover at various resonance widths. It is found that the superfluid transition temperature T-c increases monotonically at all widths as the effective interaction between atoms becomes more attractive. Furthermore, a residue factor Z(m) of the molecule's Green function and a complex effective mass have been determined to characterize the fraction and lifetime of Feshbach molecules at T-c. Our many-body calculations of Z(m) agree qualitatively well with recent measurments of the gas of Li-6 atoms near the broad resonance at 834 G. The crossover from narrow to broad resonances has also been studied.

FT-Raman studies of a range of polyimides subjected to high-energy Radiations at room and elevated temperatures

A range of polyimides have been subjected to electron beam radiolysis at different temperatures. These polyimides were chemically designed to suit space applications, being either transparent or having groups which provide oxidation resistance. The structural changes that occur in the polyimides, when subjected to electron beam irradiation doses up to 18.5 MGy and up to temperatures close to their glass transition temperatures, were studied using FT-Raman spectroscopy. The range of polyimides studied included a series of perfluoropolyimides, a silicon-modified polyimide, and Ultem. The changes in the Raman peak intensities of the different groups indicated scission reactions involving the imide rings and ether linkages. (c) 2006 Wiley Periodicals, Inc.

Strong electronic correlations in superconducting organic charge transfer salts

We review the role of strong electronic correlations in quasi-two-dimensional organic charge transfer salts such as (BEDT-TTF)(2)X, (BETS)(2)Y, and beta'-[Pd(dmit)(2)](2)Z. We begin by defining minimal models for these materials. It is necessary to identify two classes of material: the first class is strongly dimerized and is described by a half-filled Hubbard model; the second class is not strongly dimerized and is described by a quarter-filled extended Hubbard model. We argue that these models capture the essential physics of these materials. We explore the phase diagram of the half-filled quasi-two-dimensional organic charge transfer salts, focusing on the metallic and superconducting phases. We review work showing that the metallic phase, which has both Fermi liquid and 'bad metal' regimes, is described both quantitatively and qualitatively by dynamical mean field theory (DMFT). The phenomenology of the superconducting state is still a matter of contention. We critically review the experimental situation, focusing on the key experimental results that may distinguish between rival theories of superconductivity, particularly probes of the pairing symmetry and measurements of the superfluid stiffness. We then discuss some strongly correlated theories of superconductivity, in particular the resonating valence bond (RVB) theory of superconductivity. We conclude by discussing some of the major challenges currently facing the field. These include parameterizing minimal models, the evidence for a pseudogap from nuclear magnetic resonance (NMR) experiments, superconductors with low critical temperatures and extremely small superfluid stiffnesses, the possible spin- liquid states in kappa-(ET)(2)Cu-2(CN)(3) and beta'-[Pd(dmit)(2)](2)Z, and the need for high quality large single crystals.

The effect of energy feedbacks on continental strength

The classical strength profile of continents(1,2) is derived from a quasi-static view of their rheological response to stress-one that does not consider dynamic interactions between brittle and ductile layers. Such interactions result in complexities of failure in the brittle-ductile transition and the need to couple energy to understand strain localization. Here we investigate continental deformation by solving the fully coupled energy, momentum and continuum equations. We show that this approach produces unexpected feedback processes, leading to a significantly weaker dynamic strength evolution. In our model, stress localization focused on the brittle-ductile transition leads to the spontaneous development of mid-crustal detachment faults immediately above the strongest crustal layer. We also find that an additional decoupling layer forms between the lower crust and mantle. Our results explain the development of decoupling layers that are observed to accommodate hundreds of kilometres of horizontal motions during continental deformation.

Strain distributionand electronic property modifications in Si/Ge axial nanowires hetrostructures

Molecular dynamics simulations were carried out for Si/Ge axial nanowire heterostructures using modified effective atom method (MEAM) potentials. A Si–Ge MEAM interatomic cross potential was developed based on available experimental data and was used for these studies. The atomic distortions and strain distributions near the Si/Ge interfaces are predicted for nanowires with their axes oriented along the [111] direction. The cases of 10 and 25 nm diameter Si/Ge biwires and of 25 nm diameter Si/Ge/Si axial heterostructures with the Ge disk 1 nm thick were studied. Substantial distortions in the height of the atoms adjacent to the interface were found for the biwires but not for the Ge disks. Strains as high as 3.5% were found for the Ge disk and values of 2%–2.5% were found at the Si and Ge interfacial layers in the biwires. Deformation potential theory was used to estimate the influence of the strains on the band gap, and reductions in band gap to as small as 40% of bulk values are predicted for the Ge disks. The localized regions of increased strain and resulting energy minima were also found within the Si/Ge biwire interfaces with the larger effects on the Ge side of the interface. The regions of strain maxima near and within the interfaces are anticipated to be useful for tailoring band gaps and producing quantum confinement of carriers. These results suggest that nanowire heterostructures provide greater design flexibility in band structure modification than is possible with planar layer growth.

Interplay between the charge transport phenomena and the charge-transfer phase transition in RbxMn[Fe(CN)6]y.zH2O

Charge transport and dielectric measurements were carried out on compacted powder and single-crystal samples of bistable RbxMn[Fe(CN)6]y·zH2O in the two valence-tautomeric forms (MnIIFeIII and MnIIIFeII) as a function of temperature (120-350 K) and frequency (10-2-106 Hz). The complex conductivity data reveal universal conductivity behavior and obey the Barton-Nakajima-Namikawa relationship. The charge transport is accompanied by dielectric relaxation that displays the same thermal activation energy as the conductivity. Surprisingly, the activation energy of the conductivity was found very similar in the two valence-tautomeric forms (0.55 eV), and the conductivity change between the two phases is governed mainly by the variation of the preexponential factor in each sample. The phase transition is accompanied by a large thermal hysteresis of the conductivity and the dielectric constant. In the hysteresis region, however, a crossover occurs in the charge transport mechanism at T < 220 K from an Arrhenius-type to a varying activation energy behavior, conferring an unusual “double-loop” shape to the hysteresis.