GRID and Multiphonon States

The development of the GRID technique for determining nuclear level lifetimes of excited low-spin states populated in thermal neutron capture reactions has resulted in the ability to perform detailed studies of proposed multiphonon excitations for the first time. This paper discusses the experimental evidence for multiphonon excitations determined using the GRID technique. In deformed nuclei several good examples of γγK^π = 4⁺ excitations have been established, whereas the experimental evidence gathered on K^π= 0⁺ bands is contradictory, and any interpretations will likely involve the mixing of several different configurations. In vibrational nuclei the GRID technique has helped to establish the existence of multiple quadrupole phonon excitations in ¹¹⁴Cd, and an almost complete set of quadrupole-octupole coupled states in ¹⁴⁴Nd.     

Analysis of Two Infrared Bands of CH2D2

Two infrared absorption bands of CH₂D₂ have been analyzed in the semirigid rotor approximation. These are the A-type band at 2671.67 cm⁻¹ and the C-type band at 4425.61 cm⁻¹. The A-type band has previously been assigned as v₃+v₉, and the C-type band is tentatively assigned as v₃+v₆ The upper state of the A-type band is perturbed presumably by the close lying level 2v₅. This interaction has not been investigated. The following values were found for the rotational constants of the ground vibrational state: A₀=4.303 cm⁻¹, B₀= 3.504 cm⁻¹, C₀= 3.049 cm⁻¹.     

Polarization dependence of the optical response in SnO2 and the effects from heavily F doping

The optical properties of intrinsic SnO₂ (TO) and fluorine doped (FTO) are characterized in terms of the dielectric function ε(ħω) = ε₁(ħω) + iε₂(ħω) by electronic structure calculations. The intrinsic TO shows intriguing absorption characteristics in the 3.0–8.0 eV region: (i) the low energy region of the fundamental band gap (3.2 < ħω < 3.9 eV), the optical transitions Г₃⁺ → Г₁⁺ (valence-band maximum to conduction-band minimum) is symmetry forbidden, and the band-edge absorption is therefore extremely weak. (ii) In the higher energy region (3.9 < ħω < 5.1 eV) the Г₅⁻ → Г₁⁺ transitions (from the second uppermost valence band) is strongly polarized perpendicular to the main c axis. (iii) Transitions with polarization axis parallel to c axis are generated from Г₂⁻ → Г₁⁺ transitions (from the third uppermost valence bands), and dominates at high energies (5.1 < ħω eV). Heavily F doped TO (FTO) with doping concentrations n_F = 4 × 10²⁰ cm^− 3 changes the absorption significantly: (iv) Substitutional F_O generates strong inter-conduction band absorption at 0.8, 2.2, and 3.8 eV which affects also the high frequency dielectric constant ε_∞. (v) Interstitial F_i is inactive as a single dopant, but act as a compensating acceptor in highly n-type FTO. This explains the measured non-linear dependence of the resistivity with respect to F concentration.     

Infrared Absorption Spectrum of Nitrous Oxide (N2O) From 1830 cm?1 to 2270 cm?1

The frequencies of the vibration-rotation spectrum of N₂O have been measured from 1830 cm⁻¹ to 2270 cm⁻¹. A number of weak bands have been measured and assigned to “hot bands’’ and isotopic species in normal abundance. By using the Ritz principle and previously measured bands the bending frequency (v₂) is calculated as 588.78₀ cm⁻¹. Frequencies are given for lines arising from the three principal transitions found in this region.     

New aspects of π–d interactions in magnetic molecular conductors

The 2 : 1 cation radical salts of bent donor molecules of ethylenedithio-tetrathiafulvalenoquinone-1,3-dithiolemethide (EDT-TTFVO), ethylenedithio-diselenadithiafulvalenoquinone-1,3-dithiolemethide (EDT-DSDTFVO), ethylenedithio-diselenadithiafulvalenothioquinone-1,3-diselenolemethide (EDT-DSDTFVSDS), ethylenedioxy-tetrathiafulvalenoquinone-1,3-dithiolemethide (EDO-TTFVO) and ethylenedioxy-tetrathiafulvalenoquinone-1,3-diselenolemethide (EDO-TTFVODS) with FeX₄⁻ (X = Cl, Br) ions are prepared by electrocrystallization. The crystal structures of these salts are composed of alternately stacked donor molecule and magnetic anion layers. The band structures of the donor molecule layers are calculated using the overlap integrals between neighboring donor molecules and are compared with the observed electronic transport properties. The magnetic ordering of the Fe(III) d spins of FeX₄⁻ ions is determined from magnetization and heat capacity measurements. The magnetic ordering temperatures are estimated by considering a combination of a direct d–d interaction between the d spins and an indirect π–d interaction between the conduction π electron and the d spins, whose magnitudes are separately calculated from the crystal structures with an extended Hückel molecular orbital method. The occurrence of a π–d interaction is proved by the negative magnetoresistance, and the magnitude of magnetoresistance reflects the strength of the π–d interaction. The effect of pressure on the magnetoresistance is studied, and the result indicates that the magnitude of magnetoresistance increases, namely, the π–d interaction is enhanced with increasing pressure. From these experimental results it is shown that (EDT-TTFVO)₂•FeBr₄ is a ferromagnetic semiconductor, (EDT-DSDTFVO)₂•FeX₄ (X = Cl, Br) and (EDT-DSDTFVSDS)₂•FeBr₄ are metals exhibiting antiferromagnetic ordering of the d spins, and (EDO-TTFVO)₂•FeCl₄ and (EDO-TTFVODS)₂•FeBr₄•(DCE)_0.5 (DCE =-dichloroethane) are genuine antiferromagnetic metals. Among them, the (EDT-TTFVO)₂•FeBr₄ salt is the first π–d molecular system where the d spins of FeBr₄⁻ ions are ferromagnetically ordered through antiferromagnetic interaction with the conduction π electrons. Corresponding to this ferromagnetic ordering, an anomalous dielectric slow-down phenomenon toward the ordering temperature is observed. The π–d interaction in (EDT-DSDTFVSDS)₂•FeBr₄ is very large and comparable to that in λ-(BETS)₂•FeCl₄, which has the highest reported value so far, while the d–d interaction is fairly small. Concerning the ratio between the magnitudes of π–d and d–d interactions (J_πd/J_dd), this salt is currently the best π–d molecular system.     

Magnetic Rotation in the A = 80 Region: M1 Bands in Heavy Rb Isotopes

We have studied the isotopes ⁸²Rb₄₅, ⁸³Rb₄₆, and ⁸⁴Rb₄₇ to search for magnetic rotation which is predicted in the tilted-axis cranking model for a certain mass region around A = 80. Excited states in these nuclei were populated via the reaction ¹¹B + ⁷⁶Ge with E = 50 MeV at the XTU tandem accelerator of the LNL Legnaro. Based on a γ-coincidence experiment using the spectrometer GASP we have found magnetic dipole bands in each studied nuclide. The regular M1 bands observed in the odd-odd nuclei ⁸²Rb and ⁸⁴Rb include B(M1)/B(E2) ratios decreasing smoothly with increasing spin in a range of 13⁻ ≤ J^π ≤ 16⁻. These bands are interpreted in the tilted-axis cranking model on the basis of four-quasiparticle configurations of the type π(fp)πg9/22νg9/2. This is the first evidence of magnetic rotation in the A ≈ 80 region. In contrast, the M1 sequences in the odd-even nucleus ⁸³Rb are not regular, and the B(M1)/B(E2) ratios show a pronounced staggering.     

Estimation of Concentration and Bonding Environment of Water Dissolved in Common Solvents Using Near Infrared Absorptivity

Integrated near infrared (NIR) absorbance has been used to determine the absorptivity of the υ₂ + υ₃ combination band of the asymmetric stretch (υ2) and the bending vibration (υ3) for water in several organic solvents. Absorptivity measured in this way is essentially constant across the absorption envelope and is found to be 336 L mol⁻¹ cm⁻¹ with a standard deviation of 4 L mol⁻¹ cm⁻¹ as estimated from a least squares fit of a straight line to data from water concentrations between 0.01 mol/L and 0.06 mol/L. Absorptivity measured from the peak maximum of the υ2 + υ3 combination band of water varies with the type of hydrogen bonding of the water molecule because the shape of the NIR absorption envelope changes with the hydrogen bonding.Because the integrated NIR absorptivity of the υ₂ + υ₃ combination band of water is essentially constant across the absorption envelope, the NIR absorption envelope reflects the distribution of hydrogen bonding of the water. The shape and location of the absorption envelope appear to be governed mostly by the number of hydrogen bonds from the water molecules to easily polarized atoms. Water that is a donor in hydrogen bonds to atoms which are not easily polarized (such as the oxygen of a typical carbonyl group) absorbs near 5240 cm⁻¹ to 5260 cm⁻¹. Water that donates one hydrogen bond to an easily polarized atom (such as a water molecule oxygen) absorbs near 5130 cm⁻¹ to 5175 cm⁻¹, and water that donates two hydrogen bonds to easily polarized atoms is estimated to absorb near 5000 cm⁻¹ to 5020 cm⁻¹. Water donating two hydrogen bonds to other water molecules may be said to be in a water-like environment. In no case does a small amount of water absorbed in a host material appear to have a water-like environment.     

X-Ray Spectrometry of Copper: New Results on an Old Subject

We review recent, and some less recent, measurements of several emission spectra of copper. The results are discussed with special emphasis on elucidating the structure of the Kα_1,2 and Kβ_1,3 diagram lines and their underlying transitions. These lines are found to contain ≈30 % contribution from 3d spectator hole transitions. Other multielectronic transitions, the 2p spectator hole (satellites) and 1s spectator hole (hypersatellites) transitions were also measured. They are discussed paying special attention to the evolution of the lineshapes and intensities from the excitation threshold to saturation. Trends in the measured quantities depending on the spectator hole’s shell and subshell are also discussed.     

Nature of intrinsic and impure luminescence of MAlP2O7 crystals

The results of the photoluminescence (PL) investigation of pure and chromium-doped MAlP₂O₇ (M = Na, K, Cs) compounds are presented. The spectra of the intrinsic luminescence of MAlP₂O₇ crystals consist of a separated UV band at a peak position near 330 nm and a complex wide band which covers the region of visible light up to 750 nm at excitation by VUV synchrotron radiation. The “red” band in 600–1000 nm diapason appears in the PL spectra of crystals doped with chromium ions. The effect of the temperature on the structure, the peak positions and intensities of the luminescence bands was studied. An assumption about the nature of the intrinsic PL was made. The “red” luminescence was considered as a result of the ⁴Т₂ → ⁴А₂ radiation transitions in the impurity Cr³⁺ ions located in the intermediate crystal field.     

A Quantum Algorithm Detecting Concentrated Maps

We consider an arbitrary mapping f: {0, …, N − 1} → {0, …, N − 1} for N = 2ⁿ, n some number of quantum bits. Using N calls to a classical oracle evaluating f(x) and an N-bit memory, it is possible to determine whether f(x) is one-to-one. For some radian angle 0 ≤ θ ≤ π/2, we say f(x) is θ − concentrated if and only if e^2πif(x)/N ? e^{i[ψ₀?θ,ψ₀+θ]} for some given ψ₀ and any 0 ≤ x ≤ N − 1. We present a quantum algorithm that distinguishes a θ-concentrated f(x) from a one-to-one f(x) in O(1) calls to a quantum oracle function U_f with high probability. For 0 < θ < 0.3301 rad, the quantum algorithm outperforms random (classical) evaluation of the function testing for dispersed values (on average). Maximal outperformance occurs at θ=12sin−11π≈0.1620 rad.     

Preparation and Calibration of Carrier-Free 209Po Solution Standards

Carrier-free ²⁰⁹Po solution standards have been prepared and calibrated. The standards, which will be disseminated by the National Institute of Standards and Technology as Standard Reference Material SRM 4326, consist of (5.1597 ±0.0024) g of a solution of polonium in nominal 2 mol · L⁻¹ hydrochloric acid (having a solution density of (1.031±0.004) g · mL⁻¹ at 22 °C) that is contained in 5 mL flame-sealed borosilicate glass ampoules, and are certified to contain a ²⁰⁹Po alpha-particle emission rate concentration of (85.42±0.29) s⁻¹ · g⁻¹ (corresponding to a ²⁰⁹Po activity concentration of (85.83 ±0.30) Bq · g⁻¹) as of the reference time of 1200 EST 15 March 1994. The calibration was based on 4πα liquid scintillation (LS) measurements with two different LS counting systems and under wide variations in measurement and sample conditions. Confirmatory measurements by 2πα gas-flow proportional counting were also performed. The only known radionuclidic impurity, based on α- and photon-emission spectrometry, is a trace quantity of ²⁰⁸Po. The ²⁰⁸Po to ²⁰⁹Po impurity ratio as of the reference time was 0.00124 ±0.00020. All of the above cited uncertainty intervals correspond to a combined standard uncertainty multiplied by a coverage factor of k = 2. Although ²⁰⁹Po is nearly a pure α emitter with only a weak electron capture branch to ²⁰⁹Bi, LS measurements of the ²⁰⁹Po a decay are confounded by an a transition to a 2.3 keV (J^π= 1/2⁻) level in ²⁰⁵Pb which was previously unknown to be a delayed isomeric state.     

Infrared Spectrum of the v2+ v6 Band of C13C12H6

The infrared spectrum of the v₂+v₆ band of C¹³C¹²H₆ has been analyzed and a value of B₀= 0.64865 ±0.00005 cm⁻¹ determined. When this value is combined with that found in recent work on isotopically normal ethane, a “r_s” value of 1.527±0.004 A for the carboncarbon bond distance is obtained. (Uncertainties are probable errors.)     

A Spectrophotometric Study of the Interaction of Uranyl Ions with Orthosilicic Acid and Polymeric Silicic Acids in Aqueous Solutions

The interaction of UO ₂ ²⁺ ions with orthosilicic acid Si(OH)₄ and polymeric silicic acids (PSAs) was studied spectrophotometrically. The equilibrium constant of the reaction UO ₂ ²⁺ + Si(OH)₄ = UO₂OSi(OH) ₃ ⁺ + H⁺ in solutions with the ionic strength I = 0.1–0.2 is log K = −2.56±0.09 (log K ⁰ = −2.29±0.09 recalculated to I = 0); the stability constant of the complex UO₂OSi(OH) ₃ ⁺ (I = 0) is log β⁰ = 7.52±0.09. Formation of small oligomers (degree of polymerization n ≤ 4) has virtually no effect on the apparent constant K. When high polymers are formed (n > 100), the apparent equilibrium constant decreases by a factor of 2–3, and the “true” equilibrium constant recalculated to the actual concentration of silanol groups increases by a factor of 3–4. The absorption spectrum of the complex UO₂OSi(OH) ₃ ⁺ was obtained by treatment of the experimental spectra; it has an absorption maximum in the visible range at 422.5 nm, ɛ_422.5 = 35±2 l mol⁻¹ cm^{− 1}. At pH higher than 5–6, complexes of UO ₂ ²⁺ with PSAs of the composition UO₂(≡SiO)₂(≡ SiOH) _{m − 2} are formed. The absorption spectrum of such a complex was obtained.__________Translated from Radiokhimiya, Vol. 47, No. 4, 2005, pp. 315–321.Original Russian Text Copyright © 2005 by Yusov, Fedoseev.     

Experimental and Theoretical Study of Kinetics of Bulk Crystallization in Poly(Chlorotrifluoroethylene)

The rate of isothermal bulk crystallization of poly(chlorotrifluoroethylene), T_m=221° C, was measured from 170° to 200° C. The intrinsic bulk crystallization, which accurately followed an n = 2 law, was shown to be a result of the injection of primary nuclei sporadically in time, with one-dimensional growth of centers derived from these nuclei. The crystallites are exceedingly small. The one-dimensional growth process was isolated by nucleating specimens with seed crystals, and its temperature-dependence determined between 191° and 205° C. The seed crystal isotherms followed an n = 1 law. The temperature coefficients of the rate of nucleation and the rate of growth were both strongly negative.A theory of homogeneous nucleation that takes into account the segmental character of the polymer chains is developed in some detail. A cylindrical nucleus is assumed. In the temperature range near the melting point, region A, where the radius and length of the nucleus are unrestricted, the rate of nucleation is shown to be proportional to exp(−α/T³ΔT²). The nucleation rate is proportional to exp (−β/T²ΔT) in region B, which extends from somewhat below the melting point to considerably lower temperatures; the length of the nucleus has a constant value l₀ in this region, but the radius is unrestricted. (In the above expressions, α and β are constants). Finally, at sufficiently low temperatures, region C is entered. Under certain circumstances, the rate of nucleation in region C will be extremely rapid, and correspond to a “nucleative collapse” of the supercooled liquid state. A calculation of the one-dimensional growth rate shows that it is proportional to exp(−γ/T²ΔT) where β=γ.A careful analysis of the experimental data obtained between 170° and 200° C clearly showed that both the rate of nucleation and the rate of growth were proportional to exp(−β/T²ΔT), and not exp(−α/T³ΔT²). The primary nucleation event was thus of type B in this interval. A detailed analysis of the data is given, and surface free energies and the dimensions of the nuclei quoted. Quenching experiments, where the polymer was crystallized well below 170° C, gave a firm indication of the existence of region C.An experimental study was made of the extremely slow crystallization process that prevailed when the degree of crystallinity became high. The onset of this stage of the crystallization was interpreted as being the result of a massive degree of impingement. This interpretation is justified by the calculations of Lauritzen, who has given a theory of impingements that predicts a pseudoequilibrium degree of crystallinity.As indicated above, the growth process originating at homogeneous nuclei is not of a three-dimensional or spherulitic character in the region of study. Such stray spherulites as do appear in this region are shown to originate at heterogeneities. The possibility that the intrinsic growth process may become three-dimensional at crystallization temperatures sufficiently near T_m is discussed.     

Franck-Condon Factors to High Vibrational Quantum Numbers III: CN

Franck-Condon factor arrays have been computed numerically to high vibrational quantum numbers for the red (A²II_i–X²Σ⁺) and violet (B²Σ⁺ – X²Σ⁺) band systems of CN.     

BiFeO3-doped (Na0.5K0.5)NbO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1−x)(Na_0.5K_0.5)NbO₃-xBiFeO₃ (x=0∼0.07) were synthesized by the solid-state reaction. Differential scanning calorimetry (DSC) measurements revealed that an increase in the amount of BiFeO₃ dopant resulted in a decrease in the orthorhombic-tetragonal and tetragonal-cubic phase transition temperature of the material. One percent BiFeO₃ additive suppressed grain growth, which not only benefits the sintering of ceramics but also enhances the piezoelectric and ferroelectric properties, where d₃₃=145pC/N, k_p=0.31, Q_m=80, P_r=11.3 μC cm⁻² and E_c=16.5 kV cm⁻¹. As x_BF>0.01, both piezoelectric and ferroelectric properties decreased rapidly with an increasing amount of dopant.     

A simple modification of the Hodgkin and Huxley equations explains type 3 excitability in squid giant axons

The Hodgkin and Huxley (HH) model predicts sustained repetitive firing of nerve action potentials for a suprathreshold depolarizing current pulse for as long as the pulse is applied (type 2 excitability). Squid giant axons, the preparation for which the model was intended, fire only once at the beginning of the pulse (type 3 behaviour). This discrepancy between the theory and experiments can be removed by modifying a single parameter in the HH equations for the K⁺ current as determined from the analysis in this paper. K⁺ currents in general have been described by I_K=g_K(V−E_K), where g_K is the membrane''s K⁺ current conductance and E_K is the K⁺ Nernst potential. However, I_K has a nonlinear dependence on (V−E_K) well described by the Goldman–Hodgkin–Katz equation that determines the voltage dependence of g_K. This experimental finding is the basis for the modification in the HH equations describing type 3 behaviour. Our analysis may have broad significance given the use of I_K=g_K(V−E_K) to describe K⁺ currents in a wide variety of biological preparations.     

Self-Broadening of Carbon Monoxide in the 2 v and 3 v Bands

The self-broadening of carbon monoxide has been measured for the 2 v and 3 v bands with pressures up to 3.5 atmospheres. A grating spectrometer of high resolving power was used for the measurements and the correction for finite slits was small. The corrections varied from 3 to 20 percent for the different conditions of measurement. The half-widths per atmosphere, γ°, decreased from 0.089 cm⁻¹ for |m| = 1 to 0.053 cm⁻¹ for |m| = 21. The half-widths are compared with those obtained by other investigators and it is shown that the results reported in this work fall in between the self-broadening values previously obtained.     

Absorption and emission properties of Ho doped lead-zinc-borate glasses

This paper reports on the affect of lead content on the absorption and emission spectra of the Ho³⁺ ion doped lead-zinc-borate glasses in the composition (mol%) of (20 − x)PbO-20ZnO-(59 + x)B₂O₃-1.0Ho₂O₃ where x = 0, 5,10,15 of PbO content with λ_exc = 405 nm. The experimental absorption band energies have satisfactorily been correlated with the theoretical results with an r.m.s deviation of zero with the following correction factors obtained by a least square fit analysis: ΔE¹ = 348.495936 cm^− 1, ΔE² = 1.436043 cm^− 1, ΔE³ =  46.481575 cm^− 1, Δξ_4f = − 28.512979 cm^− 1, Δα = 55.508936 cm^− 1, Δβ = − 1394.339908 cm^− 1 and Δγ = 1208.424336 cm^− 1. By applying the Judd-Ofelt intensity parameter Ω₂ has been found to be linearly decreasing with the PbO content from 5 to 10 mol% and then increasing. And also radiative (A, A_T, β, τ_r) characteristic factors of the luminescent transitions (⁵I₈ ← ⁵F_3,4,5 and ⁵S₂) of the glasses have been evaluated. Stimulated emission cross-sections (σ_p^E) of the measured emission transitions of holmium glasses have also been computed.     

High-temperature resistivity and thermoelectric properties of coupled substituted Ca3Co2O6

Polycrystalline samples of Ca_3−xNa_xCo_2−xMn_xO₆ (x=0.0–0.5) have been prepared by the sol-gel cum combustion method using sucrose in order to investigate the effects of the coupled substitution of Na and Mn on Ca and Co sites on the transport properties of Ca₃Co₂O₆(Co326). The products were characterized by Fourier transform infrared spectroscopy, powder x-ray diffraction (XRD), thermogravimetry (TGA), differential thermal analysis and scanning electron microscopy. XRD patterns reveal the formation of single-phase products up to x=0.5. Coupled substitution increases the solubility of both Na and Mn on Ca and Co sites, respectively, in contrast to the limited solubility of Na and Mn (x=0.2) when separately substituted. TGA confirms the formation of the Ca₃Co₂O₆ phase at temperatures ∼720 °C. The grain size of the parent and substituted products is in the range 150–250 nm. Electrical resistivity and Seebeck coefficient were measured in the temperature range 300–800 K. Resistivity shows semiconducting behavior for all the compositions, particularly in the low-temperature regime. The Seebeck coefficient increases with temperature throughout the measured temperature range for all compositions. The maximum Seebeck coefficient (200 μV K⁻¹) is observed for x=0.5 at 825 K, and this composition may be optimal for high-temperature thermoelectric applications.