Photophysics and Electrochemistry of some Thione Far-Red/Near-IR Triplet Emitters

The photophysics and cyclic voltammetry of two novel phosphorescent thiones, 2,2-dimethyl-indan-1-one-3-thione (DMIKT) and 2,2-dimethyl-indan-1,3-dithione (DMIDT), and three known phosphorescent thiones, 4H-pyran-4-thione (PT), 4H-1-benzopyran-4-thione (BPT) and 2,2-dimethylindan-1-thione (DMIT), have been characterised and compared. The phosphorescence emission of DMIT, DMIKT and DMIDT extends from the red into the near-IR spectral region. The additional carbonyl or thione group of DMIKT and DMIDT causes a significant shift in the emission maxima to 680 nm compared to that of DMIT, at 637 nm, in perfluorinated hydrocarbons. In acetonitrile the emission maxima of DMIKT and DMIDT are at 696 and 706 nm, respectively, and the spectra show vibronic bands which extend out beyond 850 nm. There is a significant reduction in triplet lifetime along this series (from 44 (±2) μs (DMIT) to 10 ((±0.8) μs (DMIKT) in perfluorinated solvents, and 8.6 (±0.5) (DMIT), 1.3 (±0.5) (DMIKT) and 0.35 (±0.07) μs (DMIDT) in acetonitrile), as well as a reduction in the rate constant for ground-state quenching of the triplet, (from 9.8 ((±0.9) to 3.5 ((±0.6) and 1.3 ((±0.2) × 10⁹ mol⁻¹ dm³ s⁻¹ for the same compounds). The addition of the C=O or C=S groups also causes a decrease in phosphorescence quantum yield with the highest emission quantum yield obtained for DMIT (Φ _P = 0.149 (±0.015)). Electrochemical studies show that while PT and BPT exhibit irreversible redox behaviour, DMIT, DMIKT and DMIDT all show at least one reversible reduction wave attributed to a one-electron process centred on the C=S moiety. The suitability of these lumophores for use in OLEDs is discussed.     

6 j symbols for $U_q (\mathfrak{s}\mathfrak{l}_2 )$U_q (\mathfrak{s}\mathfrak{l}_2 ) and non-Euclidean tetrahedra

We relate the semiclassical asymptotics of the 6j symbols for the quantized enveloping algebra at q a root of unity (resp. q real positive) to the geometry of spherical (resp. hyperbolic) tetrahedra.     

Note on Monte Carlo methods without necessary detailed balance

Simple criteria for convergence of Monte Carlo algorithms not necessarily requiring detailed balance for any specified transition probability are derived and it is shown that it is possible to view the algorithm as a superimposition of a Brownian motion on configurational space coupled to the transition probabilities. As such, the error contributions due to a particular Monte Carlo algorithm and the integration limits in configuration space must be distinguished from those due to the nonuniform sampling of the Brownian motion, and criteria related to the number of steps required to distinguish these errors are provided for the simplest cases involving one dimension and symmetrical probability distributions.     

A Method for Accurate Calculation ofB1Fields in Three Dimensions. Effects of Shield Geometry on Field Strength and Homogeneity in the Birdcage Coil

A method for calculatingB₁field strength and homogeneity as functions of radiofrequency shield geometry is presented. The method requires use of three-dimensional finite-element analysis, birdcage-coil theory, and antenna-array theory. Calculations were performed for a 12-element birdcage coil (19 cm diameter, 21 cm length) at 125 MHz. CalculatedB₁field strengths and homogeneities for the coil in 25 different shields and in no shield are given. For configurations where the shield is longer than the coil, bothB₁field strength and homogeneity decrease as shield diameter decreases or as shield length increases. In configurations where the shield is shorter than the coil and has a diameter of 25.6 cm,B₁homogeneity is greater than in an unshielded coil.B₁field strength was measured experimentally at 125 MHz in a birdcage coil of the same geometry as the model within shields of four different diameters. Calculated results very closely matched experimental measurement.     

Guaranteeing total balance in Metropolis algorithm Monte Carlo simulations

The condition of detailed balance has long been used as a proxy for the more difficult-to-prove condition of total balance, which along with ergodicity is required to guarantee convergence of a Markov Chain Monte Carlo (MCMC) simulation to the correct probability distribution. However, some simple-to-program update schemes such as the sequential and checkerboard Metropolis algorithms are known not to satisfy detailed balance for such common systems as the Ising model.     

Ultrahigh pressure equation of state of tantalum to 310 GPa

ABSTRACT

The isothermal compression of transition metal tantalum (Ta) was studied in a diamond anvil cell by X-ray diffraction utilizing rhenium (Re) and gold (Au) as internal X-ray pressure standards. The Re pressure marker was employed during non-hydrostatic compression to pressures up to 310?GPa while the Au pressure marker was used during quasi-hydrostatic compression in a neon pressure-transmitting medium to 80?GPa. Two ultra-high pressure experiments were conducted on Ta and Re mixtures utilizing focused-ion beam machined toroidal diamond anvils with central flats varying from 8 microns to 16 microns in diameter. The Ta metal was observed to be stable in the body-centered-cubic phase to a volume compression V/V₀?=?0.581. The measured equations of state (EOS) of Ta using two different calibrations of the Re pressure marker are compared with the ambient temperature isotherm derived from shock compression data. We provide a detailed analysis of EOS fit parameters for Ta under quasi-hydrostatic and non-hydrostatic conditions.     

Cochlear nonlinearity between 500 and 8000 Hz in listeners with normal hearing

Cochlear nonlinearity was estimated over a wide range of center frequencies and levels in listeners with normal hearing, using a forward-masking method. For a fixed low-level probe, the masker level required to mask the probe was measured as a function of the masker-probe interval, to produce a temporal masking curve (TMC). TMCs were measured for probe frequencies of 500, 1000, 2000, 4000, and 8000 Hz, and for masker frequencies 0.5, 0.7, 0.9, 1.0 (on frequency), 1.1, and 1.6 times the probe frequency. Across the range of probe frequencies, the TMCs for on-frequency maskers showed two or three segments with clearly distinct slopes. If it is assumed that the rate of decay of the internal effect of the masker is constant across level and frequency, the variations in the slopes of the TMCs can be attributed to variations in cochlear compression. Compression-ratio estimates for on-frequency maskers were between 3:1 and 5:1 across the range of probe frequencies. Compression did not decrease at low frequencies. The slopes of the TMCs for the lowest frequency probe (500 Hz) did not change with masker frequency. This suggests that compression extends over a wide range of stimulus frequencies relative to characteristic frequency in the apical region of the cochlea.     

Properties of gravitationally bound dark compact ultra dense objects

We consider compact astrophysical objects formed from dark matter fermions of mass 250 GeV to 100 TeV or from massless fermions hidden by vacuum structure of similar energy scale. These objects have maximum stable masses of sub-planetary scale and radii of micron to centimeter scale. We describe the surface gravity and tidal forces near these compact ultra dense objects, as pertinent to signatures of their collisions with visible matter objects.     

Axioms for a local Reidemeister trace in fixed point and coincidence theory on differentiable manifolds

We give axioms which characterize the local Reidemeister trace for orientable differentiable manifolds. The local Reidemeister trace in fixed point theory is already known, and we provide both uniqueness and existence results for the local Reidemeister trace in coincidence theory.