Temperature dependence of the Knight shift for cadmium in palladium

The Knight shift and its temperature dependence for a Cd impurity in palladium metal were measured by means of DPAD- and DPAC-methods utilizing the well known 5/2⁺, 247-keV state in¹¹¹Cd. The shift at 80 K was found to be KS (CdPd, 80 K)=?0.8(2)%. The observed variation of the KS in the temperature range from 80 K up to 1400 K is 0.5%. For calibration purposes an accurate remeasurement of the magnetic moment of the 5/2⁺ state in¹¹¹Cd was necessary and yieldedμ(¹¹¹Cd, 5/2⁺, 247 keV)=?0.7697(20) n.m.     

Dependence of intramolecular valence delocalization on crystal form in mixed-valence trinuclear iron phenylacetate [Fe 2 III FeIIO(PhCH2CO2)6(py)3]

A dependence of intramolecular valence delocalization on crystal form in mixed-valence trinuclear iron phenylacetate [Fe ₂ ^III Fe^IIO(PhCH₂CO₂)₆(py)₃] was found. This complex was obtained in two different crystal forms: a columnar and a needle crystal form. Mössbauer spectra of the columnar crystals show a temperature-dependent valence delocalization, while the needle crystals show a trapped mixed-valence state from a lower temperature up to room temperature.     

57Fe-Mössbauer spectroscopic studies on the mixed-valence states of oxo-centered trinuclear iron(II,III, III) complexes with fatty acid anions

Oxo-Centered mixed-valence trinuclear Iron butyrates, [Fe₃O(C₃H₇CO₂)₆(py)₃]·x(py); x=0, 1, were newly synthesized and their Mössbauer spectra were determined. The temperature dependent mixed-valence state was observed in both the pyridine-solvated and the non-solvated complexes.     

Potentiodynamic desorption spectra of metallic monolayers of Cu,Bi, Pb,Tl, and Sb adsorbed at (111), (100), and (110) planes of gold electrodes

The formation of metallic adsorption layers was studied in solutions of Cu²⁺, Bi³⁺, Pb²⁺, Tl⁺ and Sb³⁺ at (111), (100) and (110) planes of gold single crystal electrodes. Potentiodynamic desorption spectra were recorded with a sweep rate of 20 mV s^?1 for all systems. Characteristic peak structures were obtained which depend strongly on the nature of the adsorbate as well as on the substrate orientation. The half width of the peaks indicates attraction and repulsion respectively for various systems. In most systems more than one peak was observed. This is explained by the formation of various ordered structures. At low coverages peak charge data obtained by integration of current/time curves yield surface concentrations which fit those of ordered structures well, e.g. c(2×2) on (100) or $\text{p(}\text{3}\text{×}\text{3}\text{)}$ R 30° on (111). The adsorption behaviour of the (110) plane is similar in all systems because atomic chains seem to be generally stable. Near the equilibrium potential of the correspondent metal electrode, ?_r = 0, a “mono-molecular” adsorption layer was found for Cu²⁺, Pb²⁺ and Bi³⁺. In the case of the small copper atom, a 1:1 adsorption was found for all planes. Larger atoms like bismuth and lead form epitactic layers at low coverages; at high coverages they form close-packed monolayers with surface concentrations independent of the substrate structure but decreasing with increasing adsorbate radius. The coulometric data for antimony and thallium are not so conclusive. Measurements with various sweep rates show that the adsorption reaction is a slow potential dependent process in various systems. The underpotential/work function correlation of Kolb, Gerischer and Przasnyski is discussed with respect to these experiments. It follows that this concept developed for polycrystalline electrodes is qualitatively valid for (110), but not clearly so for (100) and (111).     

73Se,an unusual PAC probe applied to the study of semiconductors

The isotope⁷³Se was produced by an (α,3n) reaction from⁷²Ge in order to study the applicability of this probe to PAC defect studies in semiconductors. Measurements before and after annealing recoil implanted samples showed that the quadrupole interaction of the 66 keV state in the daughter isotope⁷³As with the lattice damage created by the implantation is comparable to that found for¹¹¹In in Ge. This indicates that⁷³Se can be a suitable probe for defect studies in semiconductors with nuclear methods.     

Si{111}晶面粒子堵塞坑的新现象

本文报道了从粒子背散射堵塞效应的实验中所发现的单晶Si的{111}晶面粒子堵塞坑的新现象。单晶Si的{111}晶面有两个面间距d_{(111)^(a)和d(111)^(b),而{110}晶面只有一个面间距d(110)。由此导致两者的堵塞坑是不同的,我们已从α粒子和质子的Si单晶堵塞效应的实验得到了证实。并由此估计了d(111)^(a)和d(111)^(b)以及d(110)的2ψ1/2角。据作者了解,到目前为止,国内外还没有人发现此现象。此现象的发现对复杂晶体的堵塞和沟道效应的研究开阔了前景。 关键词：}     

NMR detected by Mössbauer-effect,applied to the system57CoFe

The ratio of the Larmor frequencies of¹¹¹Cd and²H has been measured in an aqueous solution of CdSO₄ with high accuracy.¹¹¹Cd chemical shifts have been investigated in aqueous solutions of CdCl₂, Cd(NO₃)₂, CdSO₄, and Cd(ClO₄)₂ as a function of concentration. Using these, the ratio of the Larmor frequencies of the¹¹¹Cd nuclei for infinite dilution relative to²H in pure D₂O is given. From this ag _I -factor for¹¹¹Cd has been derived and has been compared with theg _I -factor of an optical pumping experiment. The resulting shielding constant is σ^*(hydrated¹¹¹Cd versus¹¹¹Cd atom)=?1.106(4) · 10^?3. This yields an atomic reference scale for all measured NMR line shifts in the liquid and solid state and the possibility of comparing experimental and theoretical shielding constants. As a consequence, the amount of the Knight shift of metallic cadmium becomes 20% larger.     

Muon decay in orbit spectra for μ???e conversion experiments

In mixed-valence manganites, the doped iron species play the roles of simultaneous probes and ruiners for the orbital order occurring in the Mn-O electronic subsystem. We investigated the Mn^3?+?-based undoped system RBaMn₂O_5.5 and the half-doped systems RBaMn₂O₆, and RBaMn₂O₅ substituting a tiny portion of Mn^3?+? sites with Fe^3?+?. Single-site M?ssbauer spectra were observed at room temperature in the charge-orbitally ordered state, i.e., below T_COO, for R=Y, Sm, Gd. Size of the rare earth ion strongly influences the quadrupole splitting in RBaMn₂O₆, but not in RBaMn₂O₅.     

Temperature dependence of electric field gradient in TbCoO3

The temperature dependence of the electric field gradient (efg) in TbCoO₃ perovskite was measured by perturbed angular correlation (PAC) technique using ¹¹¹Cd and¹⁸¹Ta nuclear probes. The radioactive parent nuclei ¹¹¹In and ¹⁸¹Hf were introduced into the compound through a chemical process during sample preparation. The electric quadrupole interactions at ¹¹¹Cd show two different sites, assigned to probe substituting Tb and Co atoms. The temperature dependence of quadrupole frequencies show sharp discontinuities which have been interpreted as thermally activated spin state transitions from low-spin ground state configuration to the intermediate-spin state and from intermediate-spin to high-spin state of Co^3?+? ion. For ¹⁸¹Ta only one interaction was observed, which was assigned to probe at Co site. Indication of a Jahn–Teller distortion, which stabilizes the intermediate-spin state with orbital ordering, is also pointed out. No magnetic order was observed till 77 K.     

TDPAC investigations of the111Cd quadrupole interaction in ternary chalcopyrite semiconductors

The quadrupole interaction at room temperature of¹¹¹Cd in CdSiP₂, CdGeP₂, and CdSnP₂ is investigated by^111mCd-TDPAC. The results are compared with those of former¹¹¹In(¹¹¹Cd) measurements. We observed axially symmetric quadrupole interactions with identical quadrupole coupling constants provided that radiation damage was annealed. This proves that also In probes are positioned at Cd-sites (A-sites) in these ternary compounds.     

Molecular and atomic adsorption states of oxygen on Cu(111) at 100–300 K

Adsorption states of oxygen on Cu(111) at 100–300 K were investigated by means of HREELS. Two molecular species were characterized by different OO stretching frequencies (v(OO)) at 610 cm⁻¹ and 820–870 cm⁻¹, which are assigned to the peroxo-like species (O²⁻₂) adsorbed in a bridged form and the one in a bidentate form bound on an atop site, respectively. The bridged peroxo species is preferred at the low coverage and the atop peroxo species becomes dominant at the higher coverage. In addition to the peaks due to the molecular oxygen, a peak assigned to v(CuO) of atomic oxygen was observed at 370 cm⁻¹ at the high coverage. The frequency of this mode was higher than the frequency reported for Cu(111) exposed to oxygen above 300 K, indicating that the adsorption state of atomic oxygen formed at 100 K is different from that above 300 K. The v(OO) modes became faint after annealing to 170 K because of O₂ dissociation. The v(CuO) mode of the atomic oxygen formed at 100 K remained up to 230 K and disappeared after annealing to 300 K. No desorption of O₂ was detected on annealing to 300 K. It was also found that vibrational spectra for adsorbed NH₃ are influenced by the adsorption states of atomic oxygen on Cu(111).     

Optical pumping of the metastable 53P0 level of ODD isotopes of cadmium

Metastable 5³P₀ atoms of ¹¹¹Cd and ¹¹³Cd are optically pumped in an atomic beam. Their magnetic resonances are observed with Landé factors g(³P₀, ¹¹¹ Cd) = (1.090±0.003) × 10^-3 and g(³P₀, ¹¹³Cd) = (1.143 ± 0.003) × 10^-3 which are 1.7 times larger than the g-factors of the 5¹S₀ ground state. This large difference arises from a slight mixing of the 5³P₀ level with the 5³P₁ and 5¹P₁ levels through the hyperfine interaction.     

Magnetic field dependence of 11B NMR in CeB6

The ¹¹B nuclear magnetic resonance in a dense Kondo system CeB₆ has been observed by the spin echo technique below 4.2 K at fixed frequencies of 2.5, 6.5, 13.33 and 18.00 MHz, which correspond to magnetic fields of 1.83, 4.76, 9.76 and 13.18 KOe for the free ¹¹B nucleus, respectively. The spectra in the phase II appeared to have two peaks in the magnetic field applied in the [111] direction, the spacing of which was found to be very small in zero external field and increased monotonically (up to 0.11 kOe at 2.6 K) with increasing field. On the other hand, the spectra in the phase III were complex. Especially, the spectra observed for [111] at 6.5 MHz were found to spread over 1.9 KOe and to have several peaks. From comparison between the experiments and the dipolar field calculation based on the recent neutron diffraction measurements, possible magnetic structures were examined for the phases II and III.     

Adsorption and coadsorption of carbon monoxide and hydrogen on Pd(111)

The adsorption and coadsorption of CO and H₂ have been studied by means of thermal desorption (TD) and electron stimulated desorption (ESD) at temperatures ranging from 250 to 400 K. Three CO TD states, labelled as β₂, β₁, and β₀ were detected after adsorption at 250 K. The population of β₂ and β₁ states which are the only ones observed upon adsorption at temperatures higher than 300 K was found to depend on adsorption temperature. The correlation between the binding states in the TD spectra and the ESD O⁺ and CO⁺ ions observed was discussed. Hydrogen is dissociatively adsorbed on Pd(111) and no ESD H⁺ signal was recorded following H₂ adsorption on a clean Pd surface. The presence of CO was found to cause an appearance of a H⁺ ESD signal, a decrease of hydrogen surface population and an arisement of a broad H₂ TD peak at about 450 K. An apparent influence of hydrogen on CO adsorption was detected at high hydrogen precoverages alone, leading to a decrease in the CO sticking coefficient and the relative population of CO β₂ state. The coadsorption results were interpreted assuming mutual interaction between CO and H at low and medium CO coverages, the “cooperative” species being responsible for the H⁺ ESD signal. Besides, the presence of CO was proved to favour hydrogen penetration into the bulk even at high CO coverage when H atoms were completely displaced from the surface.     

A study of branching ratios of cross sections in the charge symmetric reactions10B(d,p)11B and10B(d,n)11C

High-spin states in¹⁵⁶Er have been populated using the (α, 8n) and (¹⁶O, 4n) reactions. In the ground state band a strong backbending effect was observed atI ^π=12⁺. Four states of a secondK=0 band with spins 9, 11, 13 and 15 were found. This second band depopulates completely into the 8⁺ and 10⁺ members of the ground state band. This is explained by the fact that the upper states of this second band are yrast states and that this band crosses the (gsb)-line atI ?11.     

Line strengths,spin-splittings,and forbidden transitions in the (101) band of 14N16O2

Measurements of line strengths in the (101) and (111)-(010) bands of ¹⁴N¹⁶O₂ have been made at a resolution of 0.02 cm^?1 in the region 2863 to 2934 cm^?1. The strength data in the (101) band were analyzed to determine a vibrational band strength and coefficients of the F factor. Each subband for K_?1 ≤ 9 was analyzed separately and all the F-factor coefficients in terms of the rotational quantum number, N, were found to be too small to be of significance. However, F was found to be dependent on K_?1 and the experimentally determined subband strengths were least-squares fitted to the expression S_v⁰·F, where S_v⁰ = 68.3 cm^?2 atm^?1 at 296 K and F = 1 + (2.899 × 10^?3)K_?1 + (4.08 × 10^?3)K_?1² ? (2.34 × 10^?4)K_?1³. The integrated strengths for the (101) and (111)-(010) bands were found to be 70.9 ± 2.3 and 2.7 ± 0.3 cm^?2 atm^?1 at 296 K, respectively. Also included in this study are measurements of line center positions in the two bands and spin-splittings in the (101) band. Recent frequency measurements of lines with K_?1 ≤ 8 in the (101) band have been made at a resolution of 0.0033 cm^?1 by V. Dana and J. P. Maillard (J. Mol. Spectrosc.71, 1–4) (1978)) for the region above 2889 cm^?1 and our values are in excellent agreement with theirs. Separations of the split lines measured in this work (K_?1 ≤ 10) agree well with calculated values using expressions which include the η_aaaaK_?1⁴ term with η′_aaaa = ?1.70 ± 0.15 × 10^?4 cm^?1 as derived for the (101) state. Three forbidden (ΔN ≠ ΔJ, ΔK_?1 = 0) transitions in the (101) band were observed with their identifications based on the agreement between measured and calculated line positions and strengths.     

Potassium and potassium oxide monolayers on the platinum (111) and stepped (755) crystal surfaces: A LEED,AES, and TDS study

The adsorption of potassium and the coadsorption of potassium and oxygen on the Pt(111) and stepped Pt(755) crystal surfaces were studied by AES, LEED, and TDS. Pure potassium adlayers were found by LEED to be hexagonally ordered on Pt(111) at coverages of θ = _K0.9–;1. The monolayer coverage was 5.4 × 10¹⁴K atoms/cm² (0.36 times the atomic density of the Pt(111) surface). Orientational reordering of the adlayers, similar to the behavior of noble gas phase transitions on metals, was observed. The heat of desorption of K decreased, due to depolarization effects, from 60 kcal/mole at θ_K <0.1, to 25 kcal/mole at θ_K = 1 on both Pt(111) and Pt(755). Exposure to oxygen thermally stabilizes a potassium monolayer, increasing the heat of desorption from 25 to 50 kcal/mole. Both potassium and oxygen were found to desorb simultaneously indicating strong interactions in the adsorbed overlayer. LEED results on Pt(111) further indicate that a planar K₂O layer may be formed by annealing coadsorbed potassium and oxygen to 750 K.     

Diborane: High resolution infrared rovibration studies of 11B2H6 and 11B2D6

Ground state rotation and quartic distortion constants were obtained for ¹¹B₂D₆ from the analysis of high resolution (～0.05 cm^?1) Fourier transform infrared spectra. The bands studied comprised the ν₁₇, ν₁₈ type A, and ν₁₄, ν₉ + ν₁₅ type C bands of ¹¹B₂H₆ and the ν₁₆, ν₁₇, ν₁₈ type A, ν₈ type B, and ν₁₄ type C bands of ¹¹B₂D₆. In the case of ¹¹B₂H₆, the authors' ground state data were combined with those of Lafferty et al. obtained from a previous study (J. Mol. Spectrosc.33, 345–367 (1970)) at comparable resolution of the ν₁₆ type A and ν₈ type B fundamentals. Information on the ground state rotational energy manifold of ¹¹B₂H₆ was accumulated up to J = 23, K_a = 18, and of ¹¹B₂D₆ up to J = 32, K_a = 22. This permitted rather precise determination of the distortion constants Δ_J⁰, Δ_JK⁰, Δ_K⁰, although δ_J⁰ and δ_K⁰ proved to be too small (< 10^?7 cm^?1) and were constrained to values calculated from the force field. Sets of upper state parameters were determined for all vibrational levels studied. Although these appear to be essentially unperturbed globally, several localized perturbations were observed and identified.     

Structural, optical and electrical properties of molybdenum-doped cadmium oxide thin films prepared by spray pyrolysis method

Molybdenum-doped cadmium oxide films were prepared by a spray pyrolysis technique at a substrate temperature of 300?°C. The effect of doping on structural, electrical and optical properties were studied. X-ray analysis shows that the undoped CdO films are preferentially oriented along the (111) crystallographic direction. Molybdenum doping concentration increases the films?? packing density and reorients the crystallites along the (200) plane. A?minimum resistivity of 4.68×10^?4????cm with a maximum mobility of 75?cm²?V^?1?s^?1 is achieved when the CdO film is doped with 0.5?wt.% Mo. The band-gap value is found to increase with doping and reaches a maximum of 2.56?eV for 0.75?wt.% as compared to undoped films of 2.2?eV.