Electronic energy transfer between dye molecules in structured solutions of H<Subscript>2</Subscript>O and D<Subscript>2</Subscript>O

The structure of H₂O+D₂O solutions was studied by correlation spectroscopy of scattered light. The correlation function and size of scatterers were both found to depend nonmonotonically on the D₂O concentration in the H₂O+D₂O mixture. Processes of transfer of electronic excitation energy between dye molecules of different types in H₂O+D₂O solutions were studied. The efficiency of these processes was found to depend extremally on the concentration of the components of the solution. A fractal distribution of the interacting dye molecules is ascertained from the experimental data. The dependence of the fractal dimensionality of the dye solutions on the D₂O concentration in the D₂O+H₂O mixture is determined.     

H<Subscript>3</Subscript>O<Stack><Subscript>2</Subscript><Superscript>-</Superscript></Stack> ions with a strong quasi-symmetrical H-bond and their hydration in aqueous solutions of NaOH and KOH

Ion-molecular interactions in aqueous solutions of NaOH (0–47.8%) and KOH (0–51.95%) are studied by multiple frustrated total internal reflection IR spectroscopy. Interpretation of the spectra and analysis of the spectral data are performed based on the results of DFT calculations (B3LYP/6-31++G(d, p)) of the characteristics of the free and double hydrated H₃O ₂ ^- ion. It is established that the changes in the IR spectra of NaOH and KOH aqueous solutions caused by increasing alkali concentration are due to the formation of H₃O ₂ ^- ions with a strong quasi-symmetrical hydrogen bond and their subsequent hydration by one or two water molecules. The influence of the cation nature on the degree of hydration of H₃O ₂ ^- ions is demonstrated. The equilibrium concentrations of monohydrate (H₃O ₂ ^- ? H₂O) and dihydrate (H₃O ₂ ^- ? 2H₂O) are calculated and their IR continuous absorption spectra are isolated.     

Kinetics of low-temperature initiation of H<Subscript>2</Subscript>/O<Subscript>2</Subscript>/H<Subscript>2</Subscript>O mixture combustion upon the excitation of molecular vibrations in H<Subscript>2</Subscript>O molecules by laser radiation

The initiation of H₂/O₂/H₂O mixture combustion when asymmetric vibrations in H₂O molecules are excited by a resonant IR laser radiation is considered. It is shown that the vibrational excitation of the molecules gives rise to new efficient channels for the formation of chemically active O and H atoms and OH radicals. As a result, the chain mechanism of combustion in the mixtures is enhanced and, as a consequence, the induction time is cut and the ignition temperature is lowered. Even at a minor radiant energy flux delivered to the gas (E_in≈2.5 J/cm²), the ignition temperature of the stoichiometric H₂/O₂ mixture containing only 5% of H₂O may become as low as 300 K.     

Molecular Simulation of H<Subscript>2</Subscript>O,CO<Subscript>2</Subscript>, and CH<Subscript>4</Subscript> Adsorption in Coal Micropores

Based on the chemical model of coal, slit micropores with different pore sizes are established and structures are optimized in the software of materials studio. As the temperature rises, absolute adsorption capacities of H₂O are slightly affected, while absolute adsorption capacities of CO₂ and CH₄ gradually decrease. As the fugacity rises, excess adsorption curves of CO₂ experience increase-decrease-gentle three stages, while the curves of CH₄ gradually decrease. With the increase of pore size, adsorption capacities of H₂O increase, while adsorption capacities of CO₂ and CH₄ gradually decrease. H₂O firstly adsorbs on the oxygen-containing functional group, so the walls of pore are the preferential area for H₂O, while CO₂ and CH₄ choose to adsorb on–C–C–, therefore the walls are the primary area for CO₂ and CH₄. Strong potential in micropores and hydrogen bond among water molecules will promote the water adsorption, while the adsorptions of CO₂ and CH₄ are only induced by the Van der Waals interaction, but the difference between adsorption density and bulk density of CO₂ and CH₄ decides the change of excess adsorption capacity.     

DFT study of BaTiO<Subscript>3</Subscript> (001) surface with O and O<Subscript>2</Subscript> adsorption

Progress of scanning tunneling microscopy (STM) allowed to handle various molecules adsorbed on a given surface. New concepts emerged with molecules on surfaces considered as nano machines by themselves. In this context, a thorough knowledge of surfaces and adsorbed molecules at an atomic scale is thus particularly invaluable. In this work, within the framework of density functional theory (DFT), we present an electronic and structural ab initio study of a BaTiO₃ (001) surface (perovskite structure) in its paraelectric phase. As far as we know the atomic and molecular adsorption of oxygen at surface is then analyzed for the first time in the literature. Relaxation is taken into account for several layers. Its analysis for a depth of at least four layers enables us to conclude that a reasonable approximation for a BaTiO₃ (001) surface is provided with a slab made up of nine plans. The relative stability of two possible terminations is considered. By using a kinetic energy cut off of 400 eV, we found that a surface with BaO termination is more stable than with TiO₂ termination. Consequently, a surface with BaO termination was chosen to adsorb either O atom or O₂ molecule and the corresponding calculations were performed with a coverage 1 on a (1×1) cell. A series of cases with O₂ molecule adsorbed in various geometrical configurations are also analyzed. For O₂, the most favorable adsorption is obtained when the molecule is placed horizontally, with its axis, directed along the Ba-Ba axis and with its centre of gravity located above a Ba atom. The corresponding value of the adsorption energy is -9.70 eV per molecule (-4.85 eV per O atom). The molecule is then rather extended since the O–O distance measures 1.829 ?. By comparison, the adsorption energy of an O atom directly located above a Ba atom is only -3.50 eV. Therefore we are allowed to conclude that the O–O interaction stabilizes atomic adsorption. Also the local densities of states (LDOS) corresponding to various situations are discussed in the present paper. Up to now, we are not aware of experimental data to be compared to our calculated results.     

Reactions C<Subscript>2</Subscript>H<Subscript>2</Subscript> + OH and C<Subscript>2</Subscript> + H<Subscript>2</Subscript>O: Ab initio study of the potential energy surfaces

The stationary points of the potential energy surfaces for the reactions C₂H₂ + OH and C₂ + H₂O are calculated using density functional theory and the coupled cluster method. The relative energies and geometric parameters of the stable intermediates and transition states are in good agreement with the results of independent studies. In most cases, the relative energies differ from the earlier published values by no more than 3 kcal/mol, whereas the rotational constants, by 1–2%. The mechanism of the reaction CCOH₂ → C₂ + H₂O is studied in detail. The possible sources of errors in the calculation methods are examined.     

Reactions of molybdenum atoms with NO,O<Subscript>2</Subscript>, N<Subscript>2</Subscript>O,and CO<Subscript>2</Subscript> molecules behind shock waves

Experimental results on the interaction of Mo atoms with various oxygen-containing molecules (NO, O₂, N₂O, and CO₂) at high temperatures (>1200 K) are presented, which are in close agreement with measurements at moderate and low temperatures. It is demonstrated that the height of the activation barrier is additionally increased for spin-forbidden reactions and that an increase in the heat of reaction causes an increase in the rate constant for a given type of reaction. For the reactions of Mo atoms with O₂ and N₂O, interpolated temperature dependences of the rate constants, based on the high-temperature measurements conducted in the present work and the published low-temperature data, are proposed.     

Four-photon laser spectroscopy of low-frequency rotational resonances of H<Subscript>2</Subscript>O molecules in the liquid phase

A clearly pronounced structure of the Rayleigh wing consisting of a great number of components is measured in the range 0–100 cm^?1 using four-photon polarization spectroscopy. The features observed are compared with the calculated IR spectra of H₂O molecules in the gas phase taken from the HITRAN database. A good correlation between the frequency positions of the observed and calculated lines points to the possibility of hindered rotation of water molecules in liquid.     

Excess thermodynamic quantities of D<Subscript>2</Subscript>O water calculated from its Raman O−D stretching spectra

Excess thermodynamic functions of D₂O water have been calculated from the vibrationally decoupled O−D stretching spectra of very dilute solutions of HOD in H₂O. Comparison of the results with reference calorimetric data for water showed a good correspondence for excess heat capacity above the melting point of ice. The excess enthalpy at the melting point also coincides well with latent heat of melting.     

Accuracy in determination of the temperature and partial pressure of CO<Subscript>2</Subscript> in CO<Subscript>2</Subscript>:N<Subscript>2</Subscript>:H<Subscript>2</Subscript>O:NO<Subscript>2</Subscript> mixtures by multiple-frequency laser probing

We present the results of analysis of the errors introduced by hot-band transitions 11¹0-01¹1, 03¹0-01¹1, 12⁰0-12⁰1 of the CO₂ molecule and the absorption lines of the H₂O and NO₂ molecules in determination of the temperature and partial pressure of CO₂, included in the gas mixture CO₂: N₂:H₂O: NO₂ at atmospheric pressure, by multiple-frequency laser probing using a CO₂ laser tunable over the lines of the 00⁰1-[10⁰0,02⁰0]_I,II ground-state laser transitions. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 6, pp. 810–815, November–December, 2007.     

Detection of SF<Subscript>6</Subscript> molecules sublimating from the surface of (CO<Subscript>2</Subscript>)<Subscript><Emphasis Type="Italic">N</Emphasis></Subscript> nanoparticles in a cluster beam by the infrared multiphoton excitation method

It has been found that SF₆ molecules captured by large van der Waals clusters (CO₂) _N (where N ≥ 10² is the number of monomers in a cluster) in intersecting molecular and cluster beams sublimate from the surface of clusters after a certain time and carry information on the velocity and temperature (internal energy) of clusters. Experiments have been carried out for detecting these molecules by means of a pyroelectric detector and the infrared multiphoton excitation method. The multiphoton absorption spectra of molecules sublimating from the surface of clusters have been obtained. The temperature of the (CO₂) _N nanoparticles in the cluster beam has been estimated using these spectra and comparing them with the infrared multiphoton absorption spectra of SF₆ in the initial molecular beam.     

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.     

Nanocrystalline Cu<Subscript>2</Subscript>O prepared under high pressures

The effect of high pressure on the structure of Cu₂O is investigated. Polycrystalline samples are treated during different periods of time at different temperatures and pressures in the vicinity of the kinetic curve of the decomposition Cu₂O → Cu+CuO. The structure of the samples subjected to thermobaric treatment is characterized by x-ray diffraction, electron diffraction structural analysis, and electron microscopy at atmospheric pressure. It is found that, upon treatment of Cu₂O at temperatures and pressures close to the decomposition region, the microstructure undergoes a transformation into the nanocrystalline state.     

Coincidence of rotational energy of H<Subscript>2</Subscript>O ortho-para molecules and translation energy near specific temperatures in water and ice

A hypothesis of the quantum nature of the specific temperatures T _s of water and ice, whose values is not random, was formulated. It was found that the quantum energy hΩ _mn of closely located rotational transitions in the ortho and para spin isomers of H₂O molecules coincides with the translation energy kT near the well-known specific temperatures T _s in ice and water. On the basis of this fact it was suggested that ortho-para conversion occurs at temperatures close to T _s upon inelastic collisions and resonance energy exchange kT _s ↔ hΩ _mn in the rotation-translation-rotation (RTR) processes. Such conversion can induce rearrangement of the H-bond set structure and repacking of H₂O molecules. The coincidence kT _s ≈ hΩ _mn was checked for ice and water at 12 known T _s, as well as for heavy water D₂O near T _s = 11.2°C (maximum density) and −140°C (glassy transition). The previously observe strong deformation of the OH Raman band near T _s = 4, 19, 36, and 76°C (maximum density, maximum surface tension, minimum heat capacity, and maximum speed of sound, respectively) was interpreted as a manifestation of the water structure rearrangement induced by H₂O ortho-para conversion.     

Cluster <Emphasis Type="Italic">ab initio</Emphasis> calculations for the C<Subscript>60</Subscript>F<Subscript>24</Subscript>, C<Subscript>60</Subscript>Cl<Subscript>24</Subscript>, and C<Subscript>60</Subscript>Br<Subscript>24</Subscript> halofullerenes

This paper reports on ab initio cluster calculations of the equilibrium geometry, electronic structure, and vibrational properties of the C₆₀, C₆₀F₂₄, C₆₀Cl₂₄, C₆₀Br₂₄ molecules.     

Statistical mechanics of cation ordering in PbSc<Subscript>1/2</Subscript>Ta<Subscript>1/2</Subscript>O<Subscript>3</Subscript> and PbSc<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> solid solutions

A model Hamiltonian for B cation ordering (Sc-Nb(Ta)) in PbSc_1/2Nb_1/2O₃ and PbSc_1/2Ta_1/2O₃ solid solutions is constructed. The parameters of the model Hamiltonian are determined from the ab initio calculation within the ionic crystal model with allowance made for the deformability and the dipole and quadrupole polarizabilities of the ions. The temperatures of the phase transition due to the ordering of the B cations are calculated by the Monte Carlo method in the mean-field and cluster approximations. The phase transition temperatures calculated by the Monte Carlo method (1920 K for PbSc_1/2Ta_1/2O₃ and 1810 K for PbSc_1/2Nb_1/2O₃) are consistent with the experimental data (1770 and 1450 K, respectively). The thermodynamic properties of the cation ordering are investigated using the Monte Carlo method.     

Cluster formation in LiNi<Subscript>0.4</Subscript>Fe<Subscript>0.6</Subscript>O<Subscript>2</Subscript>

The structure of an LiNi_0.4Fe_0.6O₂ cubic solid solution is determined using magnetic measurements and electron diffraction. It is found that this solid solution has a microinhomogeneous structure due to the formation of superparamagnetic clusters. The electron diffraction analysis of LiNi_0.4Fe_0.6O₂ samples has revealed diffuse scattering characteristic of the substitutional short-range order in ordered solid solutions with a B1-type structure. It is shown that the short-range order is associated with the LiNiO₂-type rhombohedral superstructure (space group \(R\bar 3m\)), i.e., with the redistribution of lithium and nickel atoms in the (111)_B1 alternating planes. The short-range order is observed in regions with a nickel content higher than the mean nickel content corresponding to the macroscopic composition.     

Mechanisms of interaction of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript> <Emphasis Type="Italic">y</Emphasis> </Subscript> with water vapor at low-temperature annealing

Abstract—The interaction of YBa₂Cu₃O_y (123) with water vapor at temperatures T ≤ 150° has been studied. It has been shown that, with an increase in temperature, the mechanism of its interaction with water changes. Near room temperature, the main process is hydrolytic decomposition. At T ~ 100°C, the absorption of water is significantly reduced, because the role of hydrolysis becomes less important and water penetrates the structure weakly and is incorporated into oxygen vacancies mainly in the form of OH–-groups, which leads to the transition of YBa₂Cu₃O_y from the tetragonal to orthorhombic phase. With an increase in temperature to 150°C, the absorption of water increases again. In this case, the main mechanism is the penetration of water to the 123 structure, which leads to splitting of Cu–O chains and a phase transition from the 123 to pseudo-124 structure. The role of different mechanisms of interaction with water essentially depends on the oxygen content in the 123 structure. At a low oxygen index (y = 6.3), the role of hydrolysis is more important, and, at y ≥ 6.5, the incorporation of water into the structure prevails. It has been revealed that, at T = 150°C, after absorption of water, YBa₂Cu₃O_6.96 becomes a proton conductor.     

Band structure of new layered superconductors BaRh<Subscript>2</Subscript>P<Subscript>2</Subscript> and BaIr<Subscript>2</Subscript>P<Subscript>2</Subscript>

The results of ab initio FLAPW-GGA computations of the band structure of two new layered low-temperature superconductors BaRh₂P₂ and BaIr₂P₂ (with a ThCr₂Si₂ tetragonal structure) are presented. As distinct from the family of the isostructural FeAs superconductors, they feature the complete replacement of the magnetic (Fe) metal by the nonmagnetic 4d (Rh) and 5d (Ir) metals. For BaRh₂P₂ and BaIr₂P₂, the energy bands, the distributions of the densities of electronic states, the Fermi surface topology, and the coefficients of the low-temperature electron specific heat and the molar Pauli paramagnetic susceptibility have been determined. An increase in T _C in the BaRh₂P₂ (1 K) → BaIr₂P₂ (2.1 K) transition can assumingly be attributed to the features of their phonon subsystem.     

Electronic structure,ferroelectricity and optical properties of CaBi<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>9</Subscript>

Using first-principles calculations based on density-functional theory in its local-density approximation, we investigated the Electronic structure, ferroelectricity and optical properties of CaBi₂Ta₂O₉ (CBT) for the first time. It is found that CBT compound has an indirect band gap of 3.114 eV and the O 2s and 2p states are strongly hybridized with the 6s states of Bi which belong to the (Bi₂O₂)²⁺ planes. The quite strong Ta–O and Bi–O hybridization is the primary source for ferroelectricity. Our results imply that the interaction between Bi and O is highly covalent. The anisotropy occurs mainly above 4 eV in the optical properties. The different optical properties have been discussed.