Penning ionization electron spectroscopy of H2O,D2O,H2S and SO2

Electron energy peak shifts and peak shapes were determined in the ionization of H₂O, D₂O, H₂S and SO₂ by Ne(³P₂) and He(2¹S, 2³S) metastable atoms. The shifts are large, especially in ionization of H₂O and D₂O into the ionic ground state and are probably mostly due to chemical interaction during the collision.In a previous paper the electron energy distribution curves for ionization of CO, HCl, HBr, N₂O, NO₂, CO₂, COS and CS₂ by helium, neon and argon metastables and the characteristics of this ionization were described¹. In this paper the series of triatomic molecules was extended to the molecules H₂O, D₂O, H₂S and SO₂. Because all these molecules have considerable dipole moments it could be expected that the peak shifts might be enhanced as compared with other triatomic molecules.     

Magnetic phase transition in (Mn0.95Ni0.05)3B4

It was found that the metallic compound (Mn_0.95Ni_0.05)₃B₄ was ferromagnetic below 195 K and antiferromagnetic between 195 and 354 K. The transition temperature from ferromagnetic to antiferromagnetic increases with increasing external magnetic field. On the other hand, the transition temperature from antiferromagnetic to paramagnetic decreases with increasing magnetic field. It is expected that the present results might be explained by the theoretical results on the coexistence of ferro- and antiferromagnetism in the itinerant electron system reported by Moriya and Usami.     

Spectral distribution of steady-state photoconductivity in amorphous As2Se3

The spectral distribution of steady-state photoconductivity has been examined for a series of bulk and evaporated samples of amorphous As₂Se₃. All bulk samples, irrespective of preparation technique or sample treatment, show a distinct shoulder in the photocurrent spectral distribution at energies near 1.4 eV. This feature is interpreted as spectroscopic evidence for the existence of a well-defined defect level in the gap of amorphous As₂Se₃. Evaporated As₂Se₃ films do not show any structure in the spectral response.     

Single orbital relaxations accompanying core ionization in the isoelectronic series CH4, NH3, H2O,HF and Ne

Single orbital contributions to the total relaxation energy accompanying core ionization are computed by means of non-empirical LCAO MO SCF calculations within the ΔSCF formalism for the isoelectronic series CH₄, NH₃, H₂O, HF and Ne. Individual contributions to the total relaxation energy associated with the valence levels of essentially core-like 2s character are also presented.     

Pressure-induced antiferromagnetism in ferromagnetic Fe51.5Rh48.5 alloy

The pressure-temperature magnetic phase diagram based on electrical resistivity measurements was determined for Fe-Rh alloys, ferromagnetic down to 4.2 K, from room temperature to the Curie point (750 K) and for pressure up to 100 kbar. A pressure-induced first order ferromagnetic-antiferromagnetic phase transition line was found with an inhomogeneous, mixed phase existing at pressures lower than 50 kbar. A new, qualitative model is proposed to explain the phase transitions, the absence of magnetic moment on Rh atoms in the AF state and the shape of the p-T diagram. The model is based on the excitonic antiferromagnetism of semimetallic Fe-Rh and it is connected with the pecularities of the electroni structure and the shape of the Fermi surface.     

X-ray photoelectron spectroscopy of TiO2 and other titanate electrodes and various standard Titanium oxide materials: Surface compositional changes of the TiO2 electrode during photoelectrolysis

Surface compositional changes were observed for TiO₂ single crystal electrodes used for photoelectrolysis of water. Surface stoichiometries of several types of TiO₂, SrTiO₃ and BaTiO₃ electrodes were characterized by XPS and compared with a variety of titanium, titanium oxide and titanium hydride standard materials. Reduction of the electrode surface in a hydrogen atmosphere results in an oxygen deficient surface composition. Photoelectrolysis at current densities of $\text{10–15}\text{mA}\text{cm}{}^2$ for periods up to 8 h appears to return the electrode surface to a nearly stoichiometric oxygen-to-metal ratio. Reduction of the titanium oxide surfaces was also observed by exposure to an argon ion beam. Analysis of the electrode surface by a combination of XPS and ion-sputter profiling was still possible by simultaneous analysis of standard materials.     

Emission spectra of polyatomic radical cations in the gas phase: Ã2Πu → X̃2Πg band systems of Cl(CC)2 Cl+, Br(

Emission spectra of the dihalodiacetylene radical cations, X(CC)₂X⁺ with X = Cl, Br and I, excited in the gaseous phase by low energy e     

The identification of two entrance channels in the reaction of metastable helium He(23S,21S) with SO2

The energy spectrum of electrons emitted in the reaction of He(2³S) and He(2¹S) with SO₂ indicates that in addition to the covalent entrance channel a strongly attractive ionic channel plays a role. We find upper limits for the well depth of the potential curve that corresponds to the latter channel of D_e ? 3.5 eV and D_e ? 4.3 eV for He(2³S) and He(2¹S) as the reaction partner, respectively. The partitioning between the two entrance channels can be understood by assuming the coupling matrix between both channels to depend strongly on the orientation of the SO₂ molecule with respect to the incident metastable He*.     

Detection of a second Br site in K2Pt(CN)4Br0.3 3.2 H2O (KCP) by 18Br and 39K NMR

By nuclear magnetic resonance we have detected between 20 and 300 K two bromine signals with a temperature-independent intensity ratio of 2.5 ± 0.3 proving the existence of a second Br site in KCP. The result is supported by the observation of three potassium signals. Thus, three types of unit cells exist: 40% contain defect water, 43% have Br in site I and 17% Br in site II.     

Magnetic properties of the rare-earth diborodicarbides (RB2C2)

The magnetic susceptibility of RB₂C₂ has been measured in the temperature range of 3–300 K. Curie-Weiss fits to the susceptibilities led to effective moments in agreement with those expected for R³⁺ ions. The RB₂C₂ (R = Ce, Nd, Sm, Gd, Tb, Er, and Tm) compounds are antiferromagnetic. Metamagnetic transitions at low fields were observed for CeB₂C₂ and TbB₂C₂. The compounds, DyB₂C₂ and HoB₂C₂, are ferromagnets with complex magnetic structures. Praseodymium borocarbide becomes a Van Vleck paramagnet at low temperature. The magnetic ordering temperatures of these compounds are discussed in terms of their crystal structure and the RKKY theory.     

Reaction rate oscillations during CO oxidation over Pt/γ-Al2O3; experimental observations and mechanistic causes

In this paper we present experimental observations of reaction rate oscillations during CO oxidation over Pt/γ-Al₂O₃ at atmospheric pressures. Based on our experimental observations and prior experimental literature on this reaction we propose a mechanistic scheme, which we believe explains in qualitative terms the oscillatory behavior exhibited by this catalytic reaction system. This mechanistic scheme involves a Langmuir-Hinshelwood reaction between adsorbed CO and oxygen and a slow formation and reduction step of an inactive surface oxide species. Our experimental observations and mechanistic ideas, furthermore, support the existence of multiple time scale phenomena for this catalytic reaction system, an idea originally suggested by Chang and Aluko.     

Adsorption and decomposition of H2O on a K-covered Pt(111) surface

The adsorption of H₂O on clean and K-covered Pt(111) was investigated by utilizing Auger, X-ray and ultra-violet photoemission spectroscopies. The adsorption on Pt(111) at 100–150 K was purely molecular (ice formation) in agreement with previous work. No dissociation of this adsorbed H₂O was noted on heating to higher temperatures. On the other hand, adsorption of H₂O on Pt(111) + K leads to dissociation and to the formation of OH species which were characterized by a work function increase, an O 1s binding energy of 530.9 eV and UPS peaks at 4.7 and 8.7 eV below the Fermi level. The amount of OH formed was proportional to the K coverage for θ_K > 0.06 whereas no OH could be detected for θ? 0.06. Dissociation of H₂O occurred already at T = 100 K, with a sequential appearance of O 1s peaks at 531 and 533 eV representing OH and adsorbed H₂O, respectively. At room temperature and above only the OH species was observed. Annealing of the surface covered with coadsorbed K/OH indicated the high stability of this OH species which could be detected spectroscopically up to 570 K. The adsorption energy of H₂O coadsorbed with K and OH on Pt(111) is increased relative to that of H₂O on Pt. The work function due to this adsorbed H₂O increases whereas it decreases for H₂O on Pt(111). The energy shifts of valence and O1s core levels of H₂O on Pt + K as deduced from a comparison of gas phase and adsorbate spectra are 2.8–4.2 eV compared to ≈ 1.3–2.3 eV for H₂O on Pt (111). This increased relaxation energy shift suggests a charge transfer screening process for H₂O on Pt + K possibly involving the unoccupied 4a₁ orbital of H₂O. The occurrence of this mode of screening would be consistent with the higher adsorption energy of H₂O on Pt + K and with its high propensity to dissociate into OH and H.     

Vibrational study of H3OUO2PO4·3 H2O (HUP) and related compounds. Phase transitions and conductivity mechanism: Part II,H3OUO2PO4·3 H2O

Infrared and Raman spectra of polycrystalline H₃OUO₂PO₄·3 H₂O (HUP) and its D and P¹⁸O₄ derivatives, in the form of dense transparent disks and wet powder, have been investigated at various temperatures in the 100–300 K region. The bands due to framework vibrations are similar to those of KUP, whereas those for the protonic species are different. OH stretching and bending bands of the oxonium ion have been identified at 2920, 1740 and 1160 cm^?1 in the low-temperature spectrum of HUP. Differential scanning calorimetry (DSC) and infrared (IR) intensity investigations show a phase transition between 274 and 260 K. The mechanism of the phase transition consists, as in the case of KUP, of ordering of the protonic species, which induces ordering of PO₄ tetrahedra. The ordering can be influenced by excess water content, stacking faults and stress (ferroelastic behaviour is evidenced). The conductivity mechanism in HUP is discussed.     

Chemical diffusivity of lithium in LiyTi1+xS2

Chemical diffusivity of lithium was measured in polycrystalline Li_yTi_1+xS₂ using current—pulse relaxation technique on Li/1M LiC1O₄ in THF/Ti_1+xS₂ cell. Excess titanium of the nonstoichiometric titanium disulfide did not so much reduce the lithium diffusivity in the interlayer region as in the case of sodium. The diffusivity varied with the amount of intercalated lithium. It had a maximum value of 5 × 10^?8cm²/s for all compounds of Ti_1+xS₂ (0?x?0.13) when the calculations were based on the geometrical surface area. It was calculated as about 3 × 10^?10cm²/s using the effective surface area.     

The ν2 band of 14NH3: A calibration standard with better than 1 × 10−4 cm−1 precision

The Fourier transform spectra and the diode laser spectra of the ν₂ band of ¹⁴NH₃ have been measured with 0.005 and 0.002 cm^?1 resolution, respectively. A simultaneous least squares analysis has been carried out of these data together with the microwave, submillimeterwave, diode-laser heterodyne, and infrared-microwave two-photon transition frequencies between the ground and the ν₂ inversion-rotation levels. A theory of the Δk = ±3n interactions in the ground and ν₂ excited states of ammonia (?. Urban, V. ?pirko, D. Papou?ek, J. Kauppinen, S.P. Belov, L. I. Gershtein, and A. F. Krupnov, J. Mol. Spectrosc.84, 288–304 (1981)) has been used in the analysis. The “smoothed” values of the ν₂ band wavenumbers can be used for calibration purposes with better than 1 × 10^?4 cm^?1 precision. On the basis of these results, a critical evaluation has been carried out of several experimental techniques of very high resolution infrared spectroscopy.     

EPR of Mn2+ in Cd(COO)2· 3H2O single crystals

The electron paramagnetic resonance spectrum of Mn²⁺ has been investigated in cadmium oxalate trihydrate single crystals at room temperature. The spectrum, recorded in the X-band, consists of a set of lines all of which correspond to a single type of environment. None of the principal axes coincides with any crystallographic axis. The spectrum is satisfactorily described by a spin Hamiltonian with a rhombic crystalline electric field. The separations of the forbidden doublets (Δm = ± 1) in different electronic transitions have been calculated and compared with the observed doublet separations.     

Molecular orbital momentum distributions and binding energies for H2O using an electron impact coincidence spectrometer

The construction and operation of an instrument which uses the techniques of coincidence counting and electron impact spectroscopy is reported for the study of molecular ionization at large momentum transfer in which the two outgoing electrons are detected at 45° to the incident beam. Variation of the incident energy provides binding-energy spectra for Xe, CH₄ and H₂O up to 45 eV. Alternatively variation of the azimuthal angle (symmetric, non-coplanar geometry) gives a measure of the electron momentum distribution for any selected orbital in the binding-energy spectrum. Momentum distributions for the four valence orbitals of H₂O are compared with various wavefunctions from the literature.     

Structure,vibrational study and conductivity of the trihydrated uranyl bis(dihydrogenophosphate): UO2(H2PO4)2·3H2O

The X-ray structure (293 K) of UO₂(H₂PO₄)₂·3H₂O has been refined (R = 0.062): M_r = 518g, space group: P2₁/c (Z = 4); $\text{a = 10.816(1)}\text{A}\text{?}$, $\text{b = 13.896(2)}\text{A}\text{?}$, $\text{c = 7.481(1)}\text{A}\text{?}$, β = 105.65(1)^°, $\text{V = 1082.7(2)}\text{A}\text{?}{}^3$; D_c = 3.17 Mg m^?3. The structure consists of infinite chains along the (101) axis with U atoms bridged by two H₂PO₄ groups. The U atom is surrounded by a pentagonal bipyramid of oxygen atoms, one of them being an equatorial water molecule. The cohesion between the chains is ensured by hydrogen bonds involving the two last water molecules. An assignment of IR and Raman bands with isotopic substitution spectra is proposed. A phase transition at 128 K was made evident by DSC and spectroscopy. The room-temperature phase is characterized by a high disorder of the OH bond orientation while in the low-temperature phase H₂O and POH species appear well oriented. The conductivity seems to occur by proton transfer and protonic-species rotation at the POH-water molecular interface between the chains. ac conductivity has been determined by means of the complex-impedance method ($\text{σ}{}_{\mathrm{<mtext>RT</mtext>}}\text{～ (3?12) × 10}{}^{\mathrm{?5}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$; E ～ 0.20 eV).     

Electrochemical determination of the lithium ion diffusion coefficient in TiS2

Long-time chronoamperometry of TiS₂ electrodes immersed in saturated LiClO₄/DMF solution was employed to investigate the charge transport processes which govern the rate of Li⁺ intercalation in TiS₂. The intercalation rate and hence, the current, appears to be controlled by the rate of Li⁺ diffusion within the TiS₂. A model has been developed which predicts the current-time behavior under the control of Li⁺ solid state diffusion. The close agreement of this model with the experimental data allows the solid state diffusion coefficient and other transport parameters (such as effective electrode area) to be evaluated from the measured average grain boundary distance. Typical TiS₂ grain boundary distances in the 3–10 μm range yield a geometric mean value of 1.3 × 10^?9 cm²/s for the solid state diffusion coefficient; this is in close agreement with previously reported diffusivities as measured by NMR spin-lattice relaxation techniques.     

Interaction of CO,CO2 and O2 with nonpolar,stepped and polar Zn surfaces of ZnO

The nonpolar (10$\text{1}$0), stepped (40$\text{4}$1) and (50$\text{5}$1), and the polar (0001) surfaces of ZnO were prepared. Stable unreconstructed nonpolar and stepped surfaces were obtained. LEED analyses showed that the step height and the step width of the stepped surfaces were similar to the theoretical values. The polar surface showed a 1 × 1 LEED pattern of six-fold symmetry after annealing at 500°C, and evidence of a more complicated pattern at 300–400°C. Temperature programmed desorption of CO resulted in the desorption of CO from the stepped and the polar surfaces. However, desorption of CO₂ was observed from the stoichiometric nonpolar surface, and no desorption from the reduced nonpolar surface. CO₂ was also observed by interacting CO with all surfaces at elevated temperatures. A total of four temperature programmed desorption peaks of CO₂, α, β, γ, and δ were observed. The α and β peaks were observed on the nonpolar and the stepped surfaces, and the γ peak was observed on the polar surface. The α peak was assigned to adsorption on a surface ZnO pair, and the β peak was assigned to adsorption on an anion vacancy or a step. While adsorbed water enhanced the β, preadsorbed methanol reduced it. O₂ adsorption was similar on the nonpolar and the stepped surfaces, but was weak on the polar surface.