Polaron hopping in olivine phosphates studied by nuclear resonant scattering

Valence fluctuations of Fe²⁺ and Fe³⁺ were studied in a solid solution of Li_xFePO₄ by nuclear resonant forward scattering of synchrotron x rays while the sample was heated in a diamond-anvil pressure cell. The spectra acquired at different temperatures and pressures were analyzed for the frequencies of valence changes using the Blume-Tjon model of a system with a fluctuating Hamil- tonian. These frequencies were analyzed to obtain activation energies and an activation volume for polaron hopping. There was a large suppression of hopping frequency with pressure, giving an anomalously large activation volume. This large, positive value is typical of ion diffusion, which indicates correlated motions of polarons, and Li⁺ ions that alter the dynamics of both.

In a parallel study of Na_xFePO₄, the interplay between sodium ordering and electron mobility was investigated using a combination of synchrotron x-ray diffraction and nuclear resonant scattering. Conventional Mossbauer spectra were collected while the sample was heated in a resistive furnace. An analysis of the temperature evolution of the spectral shapes was used to identify the onset of fast electron hopping and determine the polaron hopping rate. Synchrotron x-ray diffraction measurements were carried out in the same temperature range. Reitveld analysis of the diffraction patterns was used to determine the temperature of sodium redistribution on the lattice. The diffraction analysis also provides new information about the phase stability of the system. The temperature evolution of the iron site occupancies from the Mossbauer measurements, combined with the synchrotron diffraction results give strong evidence for a relationship between the onset of fast electron dynamics and the redistribution of sodium in the lattice.

Measurements of activation barriers for polaron hopping gave fundamental insights about the correlation between electronic carriers and mobile ions. This work established that polaron-ion interactions can alter the local dynamics of electron and ion transport. These types of coupled processes may be common in many materials used for battery electrodes, and new details concerning the influence of polaron-ion interactions on the charge dynamics are relevant to optimizing their electrochemical performance.

Photoelectrochemistry of GaAs and Si liquid junctions

A quantitative study has been performed on the stability of GaAs surfaces in a 0.10 M K₂Se-0.01 M K₂Se₂ aqueous solution. In this electrolyte, n-type GaAs electrodes displayed significant photocorrosion in competition with faradaic charge transfer to Se^2-. Chemisorption of group VIIIB metal ions onto the GaAs surfaces yielded improved current-voltage behavior of the GaAs photoanodes, and also resulted in a significant reduction in photocorrosion. This behavior implies that the chemisorbed metal ions act to increase the rate of hole transfer to the Se^2- species. Related experiments on n-GaAs, pGaAs, and Sn-doped In₂O₃ electrodes in Te^2-/- aqueous solutions have also been performed.

The majority carrier (electrons) transfer rate constant at a highly doped n⁺-Si/Co(Cp)₂Cl-methanol junction has been measured directly using the chronoamperometry electrochemical technique. The reduction reaction rate of Co(Cp)₂+ was 0.03 cm-s^-1 at the Si electrode, and was more than 100 times slower than at a hanging mercury electrode. The slower rate was attributed to the smaller optical and static dielectric constants, and the lower density of electrons of the semiconductor. The experimental results were compared to the Marcus theory of charge transfer.

The unique properties of high purity Si/liquid junctions have been investigated under illumination conditions in which the photogenerated carrier concentration exceeds the dopant concentration. Under these high injection conditions, negligible electric fields exist at the semiconductor/liquid interface, and carrier motion is driven by diffusion. Studies of the current-voltage properties of the Si in methanol solutions containing various redox couples suggested that high efficiency photoelectrochemical cells could be established through selective collection of carriers at the semiconductor/liquid junction. The quasi-Fermi levels of electrons and holes were measured directly against the solution potential. Steady-state and transient photovoltage measurements, and theoretical modeliug of the carrier transport, generation, and recombination dynamics indicated that the quasi-Fermi levels were flat across the semiconductor sample. The recombination velocities at the Si/liquid junctions have also been measured, and were shown to vary with the solution potential following the Shockley-Read-Hall theory on recombination.

Energy loss of light ions channeling in silicon

Experimental measurements of rate of energy loss were made for protons of energy .5 to 1.6 MeV channeling through 1 μm thick silicon targets along the <110>, <111>, and <211> axial directions, and the {100}, {110}, {111}, and {211} planar directions. A .05% resolution automatically controlled magnetic spectrometer was used. The data are presented graphically along with an extensive summary of data in the literature. The data taken cover a wider range of channels than has previously been examined, and are in agreement with the data of F. Eisen, et al., Radd. Eff. 13, 93 (1972).

The theory in the literature for channeling energy loss due to interaction with local electrons, core electrons, and distant valence electrons of the crystal atoms is summarized. Straggling is analyzed, and a computer program which calculates energy loss and straggling using this theory and the Moliere approximation to the Thomas Fermi potential, V_TF, and the detailed silicon crystal structure is described. Values for the local electron density Z_loc in each of the channels listed above are extracted from the data by graphical matching of the experimental and computer results.

Zeroth and second order contributions to Z_loc as a function of distance from the center of the channel were computed from ∇²V_TF = 4πρ for various channels in silicon. For data taken in this work and data of F. Eisen, et al., Rad. Eff. 13, 93 (1972), the calculated zeroth order contribution to Z_loc lies between the experimentally extracted Z_loc values obtained by using the peak and the leading edge of the transmission spectra, suggesting that the observed straggling is due both to statistical fluctuations and to path variation.

Concentrations of major ions in the stream water of the River Duddon, England, 1970-1974 [Dataset]

This dataset provides raw data of chemical analyses made during studies on seasonal variations of some major ions in the stream water of the River Duddon in Cumbria. Measurements of sodium, calcium, potassium, magnesium and chloride ions and pH were taken at 5 stations in the River Duddon between January 1970 and August 1974.

Concentrations of major ions in the stream water of the upper basin of the River Duddon, England, 1972-1974 [Dataset]

This dataset provides raw data of chemical analyses made during studies on seasonal variations of some major ions in the stream water of the upper basin of the River Duddon in Cumbria. Measurements of sodium, calcium, potassium, magnesium and chloride ions and pH were taken at 26 stations in the River Duddon basin between 1972 and 1974.

Major ions in 25 frequently sampled tarns in the English Lake District (1954-56, 1974-1976) [Dataset]

This dataset provides raw data of chemical analyses made during studies on seasonal variations of 25 frequently sampled tarns in Cumbria. Measurements of sodium, calcium, potassium, magnesium, pH, chloride ions, alkalinity, sulphite, strong acids and nitrate were taken between 1954 and 1956 and between 1974-1976.

Concentrations of major ions in 182 tarns in the English Lake District (1953-1978) [Dataset]

This dataset provides raw data of chemical analyses made during studies on seasonal variations of 182 tarns in the English Lake District, Cumbria. Measurements of sodium, calcium, potassium, magnesium, pH, chloride ions, alkalinity, sulphite, strong acids and nitrate were taken between 1953 and 1978.

Digital-Analog Quantum Simulation of Spin Systems in Trapped Ions

65 p.

掺铒碲钨酸盐玻璃及其平面波导

研制了一种用于宽带波导放大器的掺铒碲钨酸盐激光玻璃材料，对玻璃热稳定性、光谱性质进行了表征，并在其上采用离子交换法制作了平面光波导．掺铒碲钨酸盐玻璃的转变温度Tg和析品开始温度Tx分别为377．1和488．5℃；荧光半高宽为52nm；应用McCumber理论，计算得出Er^3+离子4I13／2→^4I15／2跃迁在峰值波长1532nm的受激发射截面为0．91×10^-20cm^2．不同条件下制作了在632．8nm处多模的平面光波导，通过拟合得到Ag^+离子在300℃的有效扩散系数De为2．82×10^-1