Absolute cross sections of electron attachment to molecular clusters. Part II: Formation of (H2O) N? , (N2O) N? , and (N2) N?

Absolute cross sections σ⁻(E, N) of electron attachment to clusters (H₂O) _N , (N₂O) _N , and (N₂) _N for varying electron energy E and cluster size N are measured by using crossed electron and cluster beams in a vacuum. Continua of σ⁻(E) are found that correlate well with the functions of electron impact excitation of molecules’ internal degrees of freedom. The electron is attached through its solvation in a cluster. In the formation of (H₂O) _N ⁻ , (N₂O) _N ⁻ , and (N₂) _N ⁻ , the curves σ⁻(N) have a well-defined threshold because of a rise in the electron thermalization and solvation probability with N. For (H₂O)₉₀₀, (N₂O)₃₅₀, and (N₂)₂₆₀ clusters at E = 0.2 eV, the energy losses by the slow electron in the cluster are estimated as 3.0 × 10⁷, 2.7 × 10⁷, and 6.0 × 10⁵ eV/m, respectively. It is found that the growth of σ⁻ with N is the fastest for (H₂O) _N and (N₂) _N clusters at E → 0 as a result of polarization capture of the s-electron. Specifically, at E = 0.1 eV and N = 260, σ⁻ = 3.0 × 10⁻¹³ cm² for H₂O clusters, 8.0 × 10⁻¹⁴ cm² for N₂O clusters, and 1.4 × 10⁻¹⁵ cm² for N₂ clusters; at E = 11 eV, σ⁻ = 9.0 × 10⁻¹⁶ cm² for (H₂O)₂₀₀ clusters, 2.4 × 10⁻¹⁴ cm² for (N₂O)₃₅₀ clusters, and 5.0 × 10⁻¹⁷ cm² for (N₂)₂₆₀ clusters; finally, at E = 30 eV, σ⁻ = 3.6 × 10⁻¹⁷ cm² for (N₂O)₁₀ clusters and 3.0 × 10⁻¹⁷ cm² for (N₂)₁₂₅ clusters. Original Russian Text ? A.A. Vostrikov, D.Yu. Dubov, 2006, published in Zhurnal Tekhnicheskoĭ Fiziki, 2006, Vol. 76, No. 12, pp. 1–15.     

Electron impact ionization of Ar n , (H2O) n , Ar n (H2O) m clusters

Signals from ions forming in a supersonic molecular beam consisting of an argon-water vapor mixture are measured as functions of the exciting electron energy in the range to 120 eV. The thresholds of electron impact excitation of (H₂O) _{n − 1}H⁺ and Ar _n (H₂O _m ⁺ clusters are determined for the first time. It is found that the proton-hydroxyl group binding energy decreases considerably both in the case of water molecule clustering and when mixed Ar _n (H₂O) _m clusters arise.     

Solvent effects for CO and H2 adsorption on Cu2O (1 1 1) surface: A density functional theory study

To investigate solvent effects, CO and H₂ adsorption on Cu₂O (1 1 1) surface in vacuum, liquid paraffin, methanol and water are studied by using density functional theory (DFT) combined with the conductor-like solvent model (COSMO). When H₂ and CO adsorb on Cu_cus of Cu₂O (1 1 1) surface, solvent effects can improve CO and H₂ activation. The H-H bond increases with dielectric constant increasing as H₂ adsorption on O_suf of Cu₂O (1 1 1) surface, and the H-H bond breaks in methanol and water. It is also found that both the structural parameters and Mulliken charges are very sensitive to the COSMO solvent model. In summary, the solvent effects have obvious influence on the clean surface of Cu₂O (1 1 1) and the adsorptive behavior.     

Effect of H2O on Na+ diffusivity in beta alumina

The effect of H₂O on Na⁺ diffusivity in polycrystalline, and single crystal, beta-alumina was investigated. We found no evidence that water affects the diffusion kinetics and conclude that H₂O is not as easily introduced as a blocking impurity into either the grain boundaries or fast conducting planes, nor is Na⁺ easily removed from the structure by leaching.     

Far-infrared absorption intensities of H2O and D2O in C6H6

Far-i.r. absorption intensities have been measured for H₂O and D₂O in C₆H₆ solutions. Beer's law plots were found to be nonlinear. From the plots, the equilibrium constants of dimer formation in benzene were estimated to be 2.4M^-1 and 3.3M^-1 for H₂O and D₂O at 20°C, respectively. Based on Onsager's reaction field and including explicitly the effect of differences in molecular size between solute and solvent molecules, the internal moment of a water molecule and the volume ratio of a molecule to a cavity were estimated from the integrated absorption intensity of a D₂O monomer in C₆H₆ as 1.98 D and 0.7, respectively     

EPR of Fe3+ ion and symmetry of [AIF5·H2O]2? complex ion in (NH4)2AIF5·H2O single crystals

We used the spin-Hamiltonian method for the analysis of the electron paramagnetic resonance (EPR) spectrum of Fe³⁺ as a probe ion in (NH₄)₂AlF₅·H₂O single crystalline basic material. The theoretical expressions for the magnetic field (at which the fine structure transition lines appear) versus the angle between the magnetic field and the axis of symmetry of the magnetic complex are also given. These values were calculated by applying the perturbation theory to the second-order terms. From the experimental results (at 300 K and 9.21 GHz), the spin-Hamiltonian parameters were deduced:D=(668±10)·10⁻⁴ T,E=(−56±10)·10⁻⁴ T,a=(−54±10)·10⁻⁴ T,F=(30±10)·10⁻⁴ T. An isotropic superhyperfine structure was evidenced for the five fluorine ions. The obtained EPR data were used to determine the local symmetry of the Al³⁺ ion. A good agreement with X-ray diffraction measurements was found.     

Static and dynamic disordered states in VO2+-doped BaCl2·2H2O crystals

From the EPR investigation, two different crystalline states were found in the VO²⁺ ion-doped BaCl₂·H₂O crystal. One is a dynamic disordered state, where the trapped VO⁺² ion exhibits hindered rotational motion in a wide temperature region. This state is transformed to a static disordered state even at ambient temperature. The orientation of the doped ion reveals random distribution in the lattice sites. Such polymorphism does not come from phase transition of the host crystal, but from the existence of the metastable state of the VO²⁺ ion trapped in the lattice. The absence of the phase transition of pure BaCl₂·2H₂O was confirmed by the measurement of ¹³⁷Ba NQR and by differential thermal analysis.     

Room-Temperature Mid-, and Far-Infrared Absorption and Electrical Properties of Intercalated GaSe and TlInS2 Crystals

We report room-temperature measurements of the mid- and far-IR absorption throughout the 400 – 4000 cm⁻¹ and 10 – 700 cm⁻¹ spectral ranges and the resistivity of layered p-GaSe and p-TlInS2 intercalated with Li⁺. Intercalation was performed by immersing Bridgman grown crystals in 0.5 M solutions of LiCl in distilled water at ambient conditions. The crystal structure and the stoichiometry of the grown crystals were determined by X-ray diffraction and XRF methods. It is shown that intercalation does not change the frequency of the IR-, and Raman active low-frequency “rigid layer” mode (GaSe), the space symmetry group or the lattice parameters of the crystals. It was found that for both crystals, the resistivity versus time dependencies are nearly the same. Three ranges in the resistivity-intercalation time dependencies were explained qualitatively. The resistivity increase due to intercalation was explained by assuming that the intercalated lithium ions act as ionized donors and compensate the host p-type crystal. The highest degree of compensation for GaSe and TlInS₂ crystals was achieved after intercalation during 12 and 10 days, respectively.     

Collisional broadening and shifting of the 211-202 transition of H2O, H2O, H2O by atmosphere gases

Broadening and shifting of the 2₁₁-2₀₂ transition of H₂¹⁶O, H₂¹⁷O, H₂¹⁸O by pressure of water, nitrogen and oxygen were precisely measured at room temperature using spectrometer with radio-acoustic detection of absorption. Shift parameters for all studied lines as well as broadening parameters of H₂¹⁷O, H₂¹⁸O lines were measured for the first time. Comparison of obtained results with previously known experimental and theoretical data is presented.     

The infrared and laser Raman spectra of K2Zn(SO4)2 · 6H2O

The Raman spectra of the single crystal of K₂Zn(SO₄)₂·6H₂O belonging toC _2h ⁵ space group in the 40–1200 cm⁻¹ region in different scattering geometries and their spectra ofthe microcrystalline salt in the 1500-50 cm⁻¹ region have been reported. The dynamics of the crystal has been described in terms of 186 phonon modes under the unit cell approximation. The weak bands in the region 400–900 cm⁻¹ have been assigned to the libratory modes of H₂O molecules in contradiction to the assignments reported by Ananthanarayanan. The ambiguities existing in the literature about the assignments ofν ₂ ^c andν ₅ ^c modes of [Zn(H₂O)₆]²⁺ have also been removed. The translatory and libratory modes of different units of the crystal have been identified and assignments are made using farir and Raman data on various isomorphous tutton salts. It has been inferred that both SO ₄ ²⁻ tetrahedron and [Zn(H₂O)₆]²⁺ octahedron undergo linear as well as angular distortions from their free state symmetries in the crystal.     

Ejection of H2O,O2, H2 and H from water ice by 0.5–6 keV H+ and Ne+ ion bombardment

The ejection of H₂O, O₂, H₂ and H from water ice at 30–140 K, bombarded by 0.5–6 keV H⁺ and Ne⁺ was studied experimentally. Neon ions in this energy range deposit their energy in the ice by nuclear collisions, whereas with protons of 0.5 to 6 keV the energy deposition mechanism shifts gradually from predominantly nuclear collisions to predominantly electronic processes. The existing theory of nuclear sputtering predicts very well the yield of ejected water molecules and the experimental results in the region of electronic processes agree well with the experimental results of Lanzerotti, Brown and Johnson. However, the major mass loss from water by ion bombardment is via the ejection of O₂, H₂ and H atoms, which exceed the ejection of water molecules. O₂ and H₂ production is markedly enhanced at temperatures exceeding ~100 K, whereas H₂O and H production are temperature independent, suggesting that O₂ and H₂ are produced in the bulk of the ice whereas H₂O and H atoms are ejected from the surface or near surface layers.     

Negative ion effects in CO2 convection laser discharges

Negative ions are computed to be formed on a time scale and in quantities such that they may be a cause of plasma instability observed in low pressure electrical discharge convection CO₂ lasers. In a typical CO₂−N₂−He−H₂O laser mixture the principal ions are CO ₃ ⁻ , CO ₄ ⁻ and H⁻ with the total negative ion densityn ₋ given by 0.1n _e <n ₋<n _e , wheren _e is the electron density: but if the gases are re-cycled or if there is an air leak NO ₂ ⁻ and NO ₃ ⁻ are formed in significant amounts andn ₋ can become greater thann _e in a time considerably less than the gas dwell time in the electrical excitation discharge. CO is effective in reducingn ₋ in a system without re-cycling, but is ineffective in a re-cycled system with the oxides of nitrogen present.     

Interaction of O2, CO2, CO,C2H4 and C2H4O with Ag(110)

The interaction of O₂, CO₂, CO, C₂H₄ AND C₂H₄O with Ag(110) has been studied by low energy electron diffraction (LEED), temperature programmed desorption (TPD) and electron energy loss spectroscopy (EELS). For adsorbed oxygen the EELS and TPD signals are measured as a function of coverage (θ). Up to θ = 0.25 the EELS signal is proportional to coverage; above 0.25 evidence is found for dipole-dipole interaction as the EELS signal is no longer proportional to coverage. The TPD signal is not directly proportional to the oxygen coverage, which is explained by diffusion of part of the adsorbed oxygen into the bulk. Oxygen has been adsorbed both at pressures of less than 10^-4 Pa in an ultrahigh vacuum chamber and at pressures up to 10³ Pa in a preparation chamber. After desorption at 10³ Pa a new type of weakly bound subsurface oxygen is identified, which can be transferred to the surface by heating the crystal to 470 K. CO₂ is not adsorbed as such on clean silver at 300 K. However, it is adsorbed in the form of a carbonate ion if the surface is first exposed to oxygen. If the crystal is heated this complex decomposes into O_ad and CO₂ with an activation energy of 27 kcal/mol(1 kcal = 4.187 kJ). Up to an oxygen coverage of 0.25 one CO₂ molecule is adsorbed per two oxygen atoms on the surface. At higher oxygen coverages the amount of CO₂ adsorbed becomes smaller. CO readily reacts with O_ad at room temperature to form CO₂. This reaction has been used to measure the number of O atoms present on the surface at 300 K relative to the amount of CO₂ that is adsorbed at 300 K by the formation of a carbonate ion. Weakly bound subsurface oxygen does not react with CO at 300 K. Adsorption of C₂H₄O at 110 K is promoted by the presence of atomic oxygen. The activation energy for desorption of C₂H₄O from clean silver is ～ 9 kcal/mol, whereas on the oxygen-precovered surface two states are found with activation energies of 8.5 and 12.5 kcal/mol. The results are discussed in terms of the mechanism of ethylene epoxidation over unpromoted and unmoderated silver.     

Surface vibrations and the nature of the adsorption state: C2H2 on Pt(111)

Molecular vibrations of C₂H₂ and C₂D₂ adsorbed on Pt(111) at 140 K and ∼300K have been measured by high resolution electron energy loss spectroscopy. The comparison of C₂H₂ and C₂D₂ spectra allows an unambiguous assignment of the observed losses to the excitation of C−H bending, C−H stretching, and C−C stretching modes of nondissociatively adsorbed acetylene. From the relative intensities of losses the hybridisation state is determined to be nearsp ². The C−C stretching frequency indicates a C−C bond order of ∼1.8.     

Vibrational analysis of NaM2OH(H2O)(MoO4)2/D2O [M=Ni,Zn]

The infrared and Raman spectra of NaNi₂OH(H₂O)(MoO₄)₂ and NaZn₂OH (H₂O)(MoO₄)₂ and their partially deuterated analogues are recorded and analysed on the basis of vibrations of MoO ₄ ²⁻ tetrahedra and H₂O molecules. The MoO ₄ ²⁻ groups are found to be more distorted in NaNi₂OH(H₂O)(MoO₄)₂ than in the other compound. Bands indicating the presence of H₃O⁺ ions are not observed in NaZn₂OH(H₂O)(MoO₄)₂ ruling out the possibility of the formulation of NaZn₂OHO(MoO₃OH)₂. Hydrogen bonds of medium strength are present in both the compounds.     

Effect of pressure on Raman spectra of SnS2 single crystals

The 2H polytype of a SnS₂ layered crystal has been studied using Raman spectroscopy at pressures of up to 5 GPa in a diamond anvil cell. The Raman frequency of the intralayer mode increases linearly with increasing pressure at baric coefficients of 5.2 cm⁻¹/GPa for P<3 GPa and 3.4 cm⁻¹/GPa for P>3 GPa. This change in the baric coefficient for Raman scattering and the available data on X-ray measurements of the compressibility of 2H-SnS₂up to 10 GPa suggest that the crystal structure undergoes a transformation at about 3 GPa.     

The infrared spectra of tutton salts 1. A comparative study of (NH4)2 M″(SO4)2·6H2O (M″=Ni,Co or Mg)

The infrared spectra of (NH₄)₂M″(SO₄)₂.6H₂O has been analysed in the region 4000–250 cm⁻¹. The dynamics of each crystal has been discussed in terms of 234 phonon modes, including 3 acoustical ones, using the unit cell approximation. The ambiguity in the assignments of the bands in the region 900–500 cm⁻¹ has been removed by assigning the bands in this region to the libratory modes of H₂O molecules. It has been concluded that the NH ₄ ⁺ and SO ₄ ²⁻ ions have a symmetry lower thanT _dand also the complex [M″(H₂O)₆]²⁺ has a symmetry lower than O _h . The hydrogen bonding is the strongest in the Ni-salt and the weakest in the Mg-salt.     

A nuclear magnetic resonance study of the phase transitions and electric quadrupole Raman processes of M5H3(SO4)4·H2O (M=Na, K, Rb, and Cs) single crystals

The spin–lattice relaxation times and spin–spin relaxation times for ¹H and M in M₅H₃(SO₄)₄·H₂O (M=Na, K, Rb, and Cs) single crystals grown using the slow-evaporation method were measured as functions of temperature. Two kinds of protons were identified in the M₅H₃(SO₄)₄·H₂O structure: acid protons and water protons. Our experimental results show that the acid and water protons in Cs₅H₃(SO₄)₄·H₂O are involved in phase transitions of this crystal, whereas neither type of proton is involved in the phase transitions of the other three crystal type (M₅H₃(SO₄)₄·H₂O; M=Na, K, and Rb). Moreover, the relaxation times for the M (=Na, K, and Rb) nuclei in these crystals were found to decrease with increasing temperature and can be described with (k=2). The T₁ results for M (=Na, K, and Rb) in M₅H₃(SO₄)₄·H₂O crystals can be explained in terms of a relaxation mechanism in which the lattice vibrations are coupled to the nuclear electric quadrupole moments.     

Study of ion–solvent interactions and activation energy of LiBr in DMSO,H<Subscript>2</Subscript>O and DMSO–H<Subscript>2</Subscript>O mixtures at various temperatures

The Jones–Dole B coefficients of the electrolyte Lithium bromide (LiBr), reference salts tetra butyl ammonium tetra phenyl borate (BU₄NBPh₄), tetra butyl ammonium bromide (BU₄NBr), and potassium chloride (KCl) in dimethylsulfoxide (DMSO), water, and DMSO–water mixtures were obtained at different temperatures range from 25 to 45 °C For this, the relative viscosities were measured for Lithium bromide (LiBr) and reference salts in DMSO, water, and DMSO–water mixtures at above-mentioned temperatures. The B coefficients of these electrolytes were behaved as structure makers in DMSO, while in H₂O and DMSO–H₂O mixtures, the B-coefficient values were less positive showing the weak structure-making effect. Ionic viscosity B coefficients allow us to assess the behavior of ions in the solvent mixtures. In this study it was observed that all the values of ionic B coefficient of (Li⁺) were positive and small showing the weak structure-making effects. It was also observed that Br⁻ ions maintain negative B coefficient values in all DMSO–H₂O mixtures, except in 60% DMSO mole fraction. From this it can be concluded that Br⁻ ion behaved as a structure breaker in water and in all DMSO–H₂O mixtures except in 60% DMSO mole fraction mixtures. The low B _± values of alkali metal ions and Br⁻ ions in water are due to the breakdown of the tetrahedral structural of water and the formation of strongly structured solvated ion. It is also observed that the values of the energy of activation of the flow for LiBr are greater in DMSO–water mixtures and in pure water than in DMSO. This may be due the presence of a network of hydrogen bonds which cause the hindrance in the flow of the solution of LiBr in DMSO–water mixtures and in pure water than in DMSO.     

UPS and XPS studies of the chemisorption of O2, H2 AND H2O on reduced and stoichiometric SrTiO3(111) surfaces; The effects of illumination

About one monolayer of Ti³⁺ species is detectable at the surface of reduced SrTiO₃(111) single crystals by XPS and UPS. O₂, H₂ and H₂O have been adsorbed in the dark and the decrease on the concentration of the Ti³⁺ species has been monitored as a function of the gas exposures. Subsequent band gap illumination partially restores the Ti³⁺ initial concentration in the cases of O₂ and H₂ exposures but not in the case of H₂O. The Ti³⁺ photogeneration on the oxygen covered surface is associated with oxygen photodesorption as indicated by XPS and UPS. UPS measurements give evidence for surface hydroxylation resulting from water and hydrogen adsorption. The activity of the stoichiometric SrTiO₃(111) crystal face for O₂ and H₂ adsorption is very low when compared with the reduced SrTiO₃ samples.