Absolute coverage and isostemc heat of adsorption of deuterium on Pt(111) studied by nuclear microanalysis

The absolute coverage (θ) of deuterium adsorbed on Pt(111) in the ranges 180< T<440 K and 5 × 10^?6 < P < 5 × 10^?2 Pa D₂ has been determined by nuclear microanalysis using the D(³He, p)⁴He reaction. From these data, the isosteric heat of adsorption (E_a) has been determined to be 67 ± 7 kJ mol^?1 at θ ? 0.3. This heat of adsorption yields values of the pre-exponential for desorption (10^?5 to 10^?2 cm² atom^?1 s^?1) that lie much closer to the normal range for a second order process than those determined from previous isosteric heat measurements. The E_a versus θ relationship indicates that the adsorbed D atoms are mobile and that there is a repulsive interaction of 6–8 kJ mol^?1 at nearest neighbour distances. At 300 K the coverage decreases to ? 0.05 monolayer (? 8 × 10¹³ D atoms cm^?2) as P→ 0, apparently invalidating a recent model of site exchange in the adsorbed layer.     

A LEED study of adsorbed neon on graphite

Neon monolayers on graphite have been investigated by high resolution LEED in the range 14.5 < T < 7.5 K and 10^?8 < p < 10^?4 Torr. The fluid-solid transition line has the form ln$\text{(}\text{p}\text{Torr}\text{)= ?}\text{A}\text{T + B}\text{,}\text{with}\text{A = 740 ± 45}\text{K and}\text{B = 31.0 ± 2.8}$. The solid is an incommensurate rotated phase whose lattice parameter decreases and rotation angle increases away from the transition line. Comparison is made with other thermodynamic and diffraction studies, and a preliminary phase diagram is constructed. Extrapolation of these data to higher temperatures and pressure suggests that this rotated solid monolayer is stable up to 23–25 K (P = 3?10 Torr) at coverage x = 1, and is stable over the range 0.88 < x < 1.0 at T = 16 K (2 × 10^?7 < p 1.5 × 10^?2 Torr). Extrapolation to lower temperatures gives the 2D triple point pressure in the range p = (0.3?3) × 10^?10 Torr. The steep slope of the fluid-solid transition line is consistent with the fluid phase having a high density (x?0.80) in the temperature range studied.     

Étude par rmn de la localisation et des mouvements des protons dans les hydrures MgH2 et Mg2NiH4

Wide line and pulsed NMR studies are reported for MgH₂; and Mg₂NiH₄ hydrides at 79 and 30 MHz in the temperature range between 100 and 500 K. Line shape data confirm a rutile type structure for MgH₂, and lead to the evaluation that 97% of the hydrogen is present in this phase, the remainder being in solid solution MgH_x, (x<0.04).Mg₂NiH₄ shows a Gaussian line, whose peak-to-peak width decreases from 6.16 to 4.28 G in the range 320–365 K. From 365 to 480 K the spectrum shows a second, narrower, line (0.85 G), implying that approximately 7% of the protons have migrated from their initial position to energetically less stable sites. The thermal behaviour of the T₁ and T₂ relaxation times shows a dramatic variation in the 320–370 K temperature range in connection with the change of the proton localization. Relaxation mechanisms can be attributed mainly to conduction electron-nucleus interactions. With rising temperature, diffusion mechanisms are also involved. A diffusion activation energy of about 0.35 eV has been determined, with a diffusion coefficient 3.45 × 10^?8 < D < 4.6 × 10^?8 cm²/s.     

The Pt(110) phase transitions: A study by rutherford backscattering,nuclear microanalysis,LEED and thermal desorption spectroscopy

The adsorbate induced (1×2) (1×1) (2×1)p1g1 phase transitions on Pt(110) have been studied by Rutherford backscattering (RBS), nuclear microanalysis (NMA), LEED and thermal desorption spectroscopy. RBS data indicate that any displacement of the surface atoms from their expected bulk-like lattice sites in the (1×2) phase is ? 0.002 nm laterally and ? 0.007 nm vertically. This contraint eliminates models for the reconstruction which involve significant lateral displacements (e.g., the paired-atom or hexagonal overlayer models). The RBS data are consistent with both the rumpled model with up/down displacements not exceeding ~0.007 nm and the missing row model with an unrelaxed surface in which the out-of-plane vibrational amplitude is slightly enhanced. A c(8×4) phase, produced by CO (or NO) exposure at T?250 K, has also been characterized by RBS which demonstrated that 0.92×10¹⁵ Pt cm^?2 move on average by ~0.017 nm laterally out-of-registry with the bulk upon formation of this phase. The values of the saturation adsorbate coverages at T?200K were determined by NMA to be 0.92 ± 0.05×10¹⁵, 1.0 ± 0.06×10¹⁵ and 1.07 ± 0.10×10¹⁵ CO molecules, NO molecules and D atoms, respectively, per cm². The value of the saturation coverage by CO (θ = 1.0) supports recent models of the (2×1)p1g1 overlayer. The isosteric heat of adsorption of CO is 160 ± 15 kJ mol^?1 in the range 0.2?θ?0.5.     

Halleffekt und anisotropie der beweglichkeit der elektronen in ZnO

Hallconstant, conductivity and Hall mobility of ZnO crystals were measured as function of temperature (4 °K < T < 370 °K) and orientation. Value and anisotropy of mobility can be explained (50 °K < T < 370 °K) by polar optical scattering, deformation potential sc., piezoelectric sc. and sc. by ionized impurities. The anisotropy of mobility is caused only by piezoelectric sc. Maximum values of μ_H are reached for μ_H ⊥ c, with 2400 cm²/V sec at 40 °K and for μ_H ¦ c with 1350cm²/Vsec at 60 °. Below 50 °K Hallconstant, conductivity and Hall mobility are influenced by impurity band conduction processes. The crystals have impurity concentration in the 10¹⁶ cm^?3 range, but they show different donor activation energies depending on growth conditions: Type I: 38,4 meV (50 °K < T < 100 °K) and Type II: 20,3 meV (50 °K < T < 100 °K) and 6 meV (25 °K < T < 50 °K).     

Critical behaviour of a uniaxial ferromagnet,ErCl3·6H2O with predominant dipolar interactions

The parallel magnetic susceptibility χ of a uniaxial ferromagnet ErCl₃·6H₂O has been measured between 0.3 and 4.2K and specially near T_c = 0.353 K. The predominant contribution to the Curie-Weiss temperature is due to the dipolar interactions. χ is proportional to ?^?γ with $\text{? =}\text{T}\text{T}{}_{\mathrm{c}}\text{?1}$ in the range 10^?3 < ? < 5 × 10^?2. The γ value, γ = 1.01 ±0.03 is consistent with the theoretical prediction for a uniaxial dipolar ferromagnet.     

Temperature dependence of the rotational life times in solid H2

We have studied the temperature dependence of the nuclear transverse and longitudinal relaxation times in solid H₂ for ortho concentrations 10^-3 < X < 10^-2 between 0.4 K and the triple point, 13.9 K. We find a striking temperature dependence in T₂ over the whole temperature range. This new effect is ascribed to a coupling between molecular rotation and lattice vibrations, which is brought into evidence by the narrow width of the spectral density of the rotational fluctuations at low X.     

Self-diffusion in a series of plastic organic solids studied by NMR

Proton nuclear magnetic resonance relaxation times and linewidth measurements have been made on five polycrystalline organic compounds, triethylenediamine, 3-azabicyclononane, norbornane, norbornylene and norbornadiene. Measurements for each sample were made throughout the plastic crystal phase. The results are analysed in terms of molecular motion. Correlation times τ and activation enthalpies for translational self-diffusion of molecules are evaluated: triethylenediamine τ=7·6×10^?19 exp (96·4/RT)s, 3-azabicyclononane τ=1·7×10^?16 exp (83·6/RT)s, norbornane for 131K<T<306 K, τ=4·6×10^?15 exp (54·5/RT)s for 306K<T<360K, τ=1·1×10^?16 exp (64·8/RT)s, norbornylene, τ=4·×10^?15 exp (48·6/RT)s and norbornadiene τ=6·8×10^?15 exp (39·9/RT)s, where R is the gas constant in units of kJ K^?1mol^?1. The results and mechanism of diffusion are discussed in relation to the thermodynamic properties of the materials.     

Thermal expansion op NbSe2 and TaS2

The lattice parameters a₀ and c₀ of the hexagonal 2H polytype of NbSe₂; have been measured over the temperature range 156–478 K for a₀, and 138–482 K for c₀. The lattice parameter c₀ of the hexagonal 2H polytype of TaS₂ has been measured between 151 and 472 K. The lattice parameters a₀ and c₀ for the octahedral 1T polytype of TaS₂ been measured between 165 and 488 K. Over these temperature ranges, the following average coefficients of thermal expansion have been measured; 2H-NbSe₂, 6.6 × 10^?6K^?1 along the a-axis, 19.9 × 10^?6 K^?1 along the c-axis; 2H-TaS₂, 15.6 × 10^?6 K^?1 along the c-axis; IT-TaS₂, 12.7 × 10^?6 K^?1 along the c-axis. The parameter c₀ of 1T-TaS₂ undergoes two transitions which may be explained in terms of charge density waves.     

Reactions of initiation of the autoignition of H<Subscript>2</Subscript>–O<Subscript>2</Subscript> mixtures in shock waves

The initiation of the autoignition of hydrogen–oxygen–argon mixtures behind reflected shock waves is studied by absorption and emission spectrophotometry in the temperature range of 960 < T < 1670 K at pressures of ~0.1 MPa. Introduction of Mo(CO)₆ additive in an amount of ~80 ppm made it possible to study the effect of O atoms on the shortening of the ignition delay time of H₂–O₂–Ar mixtures. A kinetic modeling of our own and published experimental data at temperatures of 930 < T < 2500 K and pressures of 0.05 < P < 8.7 MPa enabled to establish how the initiation reactions influence the process of self-ignition and to evaluate the rate constant for one of the initiation reactions: k(H₂ + O₂ → 2OH) = (3 ± 1) × 10¹¹exp(–E _a/RT), cm³ mol^–1 s^–1, where E _a = (40 ± 2) kcal/mol.     

Low temperature thermal properties of PbI2

The heat capacity and thermal conductivity of a large (56.5 g) crystal of PbI₂ have been measured in the temperature region 0.5 < T < 3.9°K. Analysis of the heat capacity data yields a value of the limiting apparent Debye characteristic temperature θ₀^c = 99.4 (±0.3)°K, which corresponds to an average lattice wave velocity of 1.151 (±0.005) × 10⁵ cm sec^?1. It is consistent with a wave velocity estimated from neutron scattering experiments, but not with one determined from Brillouin spectra. The heat capacity data also show that dispersion of the low frequency waves is not unusual, as might have been expected for a layer-type crystal. The apparent thermal conduction is found to be surprisingly small in the crystal.     

Heat capacity of Ar monolayer adsorbed on basal plane graphite

The specific heat of Ar monolayer film adsorbed on basal planes of graphite has been measured for film coverage ranging from 0.31 to 0.97 monolayers for 4.2 < T < 68 K. It is found that a broad specific heat peak centered around 50 K exists over most of the submonolayer coverages until reaching monolayer completion. A comparison with recent neutron scattering and LEED studies relates the anomaly to a possible higher order phase transition between 2D solid and 2D fluid.     

Conductivity enhancement in fluorite-structured Ba1−xLaxF2+x solid solutions

The ionic conductivity of single crystals of the fluorite-structured solid solutions Ba_1?xLa_xF_2+x(10^?3 <×<0.45) has been studied as a function of temperature and composition in the range 300–900 K. Three regions can be discerned in the concentration dependence of the ionic conductivity: a dilute concentration region (x<10^?3), where classic relations between solute content and ionic conductivity hold; an intermediate concentration region (10^?3<x?5×10^?2), where large changes occur in the conductivity activation enthalpy and the magnitude of the conductivity; and a concentrated solid solution region (x?5×10^?2) characterized by enhanced ionic motion. In the dilute region the migration enthalpy for interstitial fluoride ions is determined to be 0.714 eV, while a value of 0.39 eV is found for the (La_BaF_i)^X association enthalpy. The defect chemistry in the intermediate concentration region is shown to be controlled by a superlinear increase of the concentration of mobile defects, while in the concentrated solid solution region a composition-independent amount of ≈1 mole% of interstitial fluoride ions with enhanced mobility, carry the current.     

Effect of electron irradiation on the paramagnetic state of La0.67Ca0.33MnO3

The effect of point defects on the magnetic properties of La_0.67Ca_0.33MnO₃ polycrystals and single crystals has been studied. The magnetic susceptibility χ _dc of the initial samples and samples irradiated by electrons to the maximum dose F = 9 × 10¹⁸ cm^?2 has been measured in the temperature region 80 K < T < 650 K. Local variations of Mn-O-Mn bond angles and lengths result in a nonmonotonic dose dependence of the Curie temperature T _C. At high doses of electron irradiation, F ≥ 5 × 10¹⁸ cm^?2, the temperature of the transition from the ferromagnetic to polaron state in a single crystal is found to increase. In the paramagnetic region close to T _C, ferromagnetically ordered polarons are observed to exist, while at T > 1.2T _C, localization of e _g electrons initiates formation of paramagnetic polarons with a higher magnetic moment. Electron irradiation stimulates persistence of magnetic polarons up to higher temperatures T > 2T _C.     

Shock-tube study of HCN self-broadening and broadening by argon for the P(10) line of the ν1 band at 3 μm

A tunable infrared diode laser was used to measure the fully resolved absorption line shape of the P(10) line in the ν₁ band (10°0–00°0) of HCN for shock-heated mixtures of HCN-Ar at temperatures of 1000, 1500 and 2000 K. The temperature dependence of the collision-broadening coefficients 2γ (cm^-1 atm^-1, FWHM) were inferred for both self-broadening and broadening by argon. For the assumed form 2γ = 2γ₀(T₀/T)ⁿ the exponent n was determined to be 0.63 ± 0.06 with 2γ₀ = 0.11 cm^-1atm^-1 and T₀ = 300 K for argon-broadening in the range 300 < T < 2000 K, and 1.2 ± 0.6 with 2γ₀ = 0.68 cm^-1atm^-1 and T₀ = 1000 K for self-broadening in the range 1000 < T < 2000 K.     

Anregung metastabiler Zustände von Barium und Thallium durch Atomstöße im Stoßwellenrohr

It is shown that relaxation times for the excitation of metastable levels of Ba and Tl by collisons of the ground state atoms with carrier gases Ne and Ar can be measured with good accuracy behind reflected shock waves (2700≦T≦3300 °K) by means of two-channel atomic line absorption spectroscopy. Quenching cross-sections, which thus can be derived, cover in principle the range 10^?14 cm²<Q<10^?21 cm². In collisions with Ar one finds for the deactivation of Ba(¹ D ₂)Q=1.2 · 10^?19cm², of Ba(³ D ₁)Q=0.95 · 10^?19 cm² and of Tl(² P _3/2)Q<5 · 10^?21 cm² without noticeable temperature dependence. From this follows a) (on the basis of the Landau-Zener formula) that the pseudo-crossing of the potential energy curves of Ba-Ar takes place within 0.25 eV of the Ba(D) levels and b) that spin-orbit coupling is not rate controlling in the Ba(³ D ₁ →¹ S ₀) transition. The ratio of cross-sections for quenching of Ba(¹ D ₂) by Ar and Ne is about 3, suggesting that the polarizabilities of the noble gas collision partners play a major rôle in the transition probabilities. The mean self-quenching cross-sectionQ=5 · 10^?16 cm² of Tl(² P _3/2) at 3000 °K is about the same as the one reported for 1000 °K and it exceeds the self-quenching cross-section of metastable Ba by at least one order of magnitude.     

The forced magnetostriction of nickel at 4.2 K

The forced volume magnetostriction of polycrystalline nickel at 4.2 K has been determined with a relative accuracy of 2 × 10^?2. Combining our result with previous data on the forced magnetostriction, we derive for the forced magnetostriction constants: h'₀ = (40 ± 1) × 10^?8T^?1, h'₁ = (-95 ± 2) × 10^?8T^?1, h'₂ = (-19 ± 2) × 10 ^?8T^?1.     

Bistability of the reaction rate in the oxidation of carbon monoxide by nitrogen monoxide on polycrystalline platinum

Multiplicity of the stationary reaction rate of CO oxidation by NO is observed under reducing conditions at pressures below 4×10^?4 mbar in the temperature range 500<T<525 K. The two branches of the reaction rate coalesce at a point where sustained oscillations are observed.     

The heat capacity of the layer compound tetrachlorobis (methylammonium) manganese—II (CH3NH3)2MnCl4, from 10 to 300k

The heat capacity of the layer compound, tetrachlorobis (methylammonium) manganese II, (CH₃NH₃)₂MnCl₄, has been measured over the range 10K <T<300K. In this region, two structural phase transitions have been observed previously by other techniques: one transition is from a monoclinic low temperature (MLT) phase to a tetragonal low temperature (TLT) phase, and the other is from TLT to an orthorhombic room temperature (ORT) phase. The present experiments have shown that the lower transition (MLT→TLT) occurs at T = 94.37±0.05K with ΔH_t = 727±5 J mol^?1 and ΔS_t = 7.76±0.05 J K^?1 mol^?1, and the upper transition (TLT→ORT) takes place at T = 257.02±0.07K with ΔH_t = 116±1J mol^?1 and ΔS_t = 0.451±0.004 J K^?1mol^?1. These results are discussed in the light of recent measurements on (CH₃NH₃)₂CdCl₄, and also with regard to a recent theoretical model of the structural phase transitions in compounds of this type.In addition to the structural phase transitions, (CH₃NH₃)₂MnCl₄ also undergoes magnetic ordering at T < 150K. The magnetic component to the heat capacity, as deduced from a corresponding states comparison of the heat capacity of the present compound with that of the Cd compound, is shown to be consistent with the behaviour expected for a quasi 2-dimensional Heisenberg antiferromagnet.