Ellipsometric study of oxygen adsorption and the carbon monoxide-oxygen interaction on ordered and damaged Ag(111)

The adsorption of oxygen on Ag(111) has been studied by ellipsometry in conjunction with AES and LEED. The oxygen pressure varied between 10^?5 and 10^?3 Torr and the crystal temperature between room temperature and 250° C. Changes in the Auger spectrum and the LEED pattern upon oxygen adsorption are very small. Oxygen coverages were derived from the changes in the ellipsometric parameter Δ. At room temperature a maximum coverage is reached within a few minutes. Its value increases with the damage produced by the preceding argon ion bombardment. The sticking coefficient derived from the initial rate of Δ-change amounts to 3 × 10^?5 for well-annealed surfaces and 2.5 ? 5 × 10^?4 for damaged surfaces. After evacuation no desorption takes place. Other types of adsorption, associated with much larger changes in Δ, were observed upon bombardment with oxygen ions and with oxygen activated by a hot filament. The reaction of CO with adsorbed oxygen was studied ellipsometrically at room temperature in the CO pressure range 10^?7–10^?6 Torr. The initial reaction rate is proportional to the CO pressure. The reaction probability (number of oxygen atoms removed per incident CO molecule) is 0.36.     

A thermodynamic theory of mechanical relaxation due to energy transfer between strain-sensitive and strain-insensitive modes in polymers

A thermodynamic theory has been developed on the relaxation strength of mechanical relaxation due to energy-transfer between strain-sensitive (intermolecular) modes and strain-insensitive (intramolecular) modes. Assuming that the strain-insensitive modes exhibit an overwhelmingly large heat capacity and function as a heat reservoir of constant temperature during the relaxation process, the relaxation strength ΔG, the difference between instantaneous and equilibrium moduli, is given as ΔG = TG² _Tα² ₁/C_z1, where T is the absolute temperature, G_T is the isothermal elastic modulus, and ₁ and C_z1 are the thermal expansion coefficient and the specific heat at constant strain of the strainsensitive modes, respectively. This assumption is reasonable for a polymeric solid in which backbone chains have a lot of vibrational degrees of freedom whose energy is rather insensitive to intermolecular distance and, on the contrary, the potential for localized motion such as motion of side chains is highly sensitive to intermolecular distance.

In a special case where the strain-sensitive modes are a set of vibrators with an angular frequency ω, ΔG = γ²C_z1T, where γ is the Grüneisen constant, defined by the strain-derivative of ω, = ?? In ω?z. The case where the strainsensitive modes are a set of rotators in an n-fold symmetrical potential can be treated as an extension of the above case. In the case where the strain-sensitive modes involve the transition between two states, ΔG in the present theory is reduced to that of the well-known two-state transition theory. Agreement is obtained between theory and experiment for a-methyl relaxation of poly(methy1 methacrylate).     

High pressure cyanide exchange study on a square-planar tetracyanometalate complex of Pt(II)

Abstract

Previous studies of cyanide exchange on square planar tetracyanoplatinate complex [Pt(CN)₄]^2- have been undertaken only at a high pH. For a more complete fundamental understanding of this system we extended the investigations of these exchanges over a large pH range. NMR kinetics methods (magnetisation transfer, isotopic exchange) proved to be very useful for obtaining quantitative rate data of the cyanide exchange on this complex. In fact it is quite significant that the reactivity of this metal center spans a ca. 9-order of magnitude range as a function of pH.

Variable temperature and variable pressure studies were undertaken in aqueous solutions and the following activation parameters obtained: ΔH? = (25.1 ± 0.4) kJmol^?1 and activation entropy ΔS? = -(142±2)JK^?1mol^?1 and activation volume ΔV? = -(27±2)cm³mol^?1.     

Kinetic and mechanistic study of the atmospheric reaction of MBO331 with Cl atoms

The present work deals with the reaction of 3-methyl-3-buten-1-ol (MBO331) with Cl atoms, which has been investigated by gas chromatography with flame ionization detection (GC-FID) at atmospheric pressure in N₂ or air, using the relative rate technique. The rate constant reaction at 298?±?1?K was found to be (5.01?±?0.70)?×?10^?10?cm³ molecule^?1?s^?1, using cyclohexane, octane and 1-butene as a reference compounds. The temperature dependence for the reaction was studied within the 298?333?K range. Additionally, a product identification under atmospheric conditions has been performed for the first time by GC-MS, with 3-methyl-3-butenal, methacrolein and chloroacetone being observed as degradation products. A theoretical study on the reaction at the QCISD(T)/6-311G**//MP2/6-311G** level was also carried out to obtain more information on the mechanism. From the theoretical study it can be predicted that Cl addition to the double bond proceeds through lower energy barriers than H-abstraction pathways and therefore is energetically favoured. Finally, atmospheric implications of the results obtained are discussed.     

Effect of temperature and high pressure on Mn2+ EPR spectra in K3H(SO4)2 fast-proton conductor

The linewidth ΔH _pp and spin-Hamiltonian parameters under temperature and high hydrostatic pressure by X-band continuous wave electron paramagnetic resonance in the K₃H(SO₄)₂ crystal were studied. Spin-Hamiltonian parameters, direction cosines and coordination of Mn²⁺ ion were determined at room temperature. The pressure at 300?MPa leads to the change of hydrogen bond potential and the transition from double well to single well potential moves about 10?K towards a higher temperature.     

Dissociation of the light-harvesting membrane protein complex I from Rhodobacter sphaeroides under high hydrostatic pressure

The light-harvesting complex 1 (LH1) from Rhodobacter sphaeroides is an excellent model system for investigating the stability of oligomeric membrane proteins under high hydrostatic pressure. The currently investigated LH1 forms a 16-meric ring structure of B825 subunits. B825 is a heterodimer of transmembrane α- and β-polypeptide chains, which non-covalently binds two bacteriochlorophyll a molecules. These pigment molecules were used as intrinsic spectroscopic sensors to follow the dissociation reaction. Our results demonstrate that the LH1 dissociates into B825 subunits through an intermediary tetrameric unit B845. The dissociation mechanism depends on pressure. At ～200–500?MPa the dissociation corresponds to a pseudo-first-order reaction, characterised by the apparent reaction rate at atmospheric pressure k₀?=?3·10^?5?s^?1, activation volume ΔV^??=??4?mL/mol, and free energy of activation ΔG^??=?26?kJ/mol. Below 200?MPa and above 500?MPa, the reaction is more complex, including further dissociation of B825 into monomers B777.     

Growth and characterization of L-phenylalanine nitric acid (LPN) and tris L-(phenylalanine)-phenylalanininum nitrate (TPLPN) as second and third order nonlinear optical materials

We synthesized noncentrosymmetric single crystals of L-phenylalanine nitrate (LPN) and tris L-(phenylalanine) L-phenylalaninium nitrate (TPLPN) by slow solvent evaporation technique. Both crystallized in monoclinic system with different acentric space groups namely P2₁ (LPN) and C2 (TPLPN) respectively. The IR and Raman spectral investigation was done for LPN and TPLPN and discussed. The UV-vis-studies accomplished the excitation wavelength of the grown crystals suitable to exhibit second harmonic generation signal. From the absorption data, remarkable optical properties such as direct band gap energy, Urbach energy, extinction coefficient were evaluated. The mechanical strength of the grown crystal was examined by Vickers micro hardness test. The temperature of decomposition was confirmed by TG/DSC analysis. Fluorescence emission spectrum of LPN and TPLPN were recorded and lifetime was also studied. The dielectric constant and dielectric loss of LPN and TPLPN has been determined as a function of frequency and temperature. Also the surface topologies of the crystallized salts were assessed by SEM studies. The third-order nonlinearities of LPN and TPLPN were determined by Z-scan technique with Nd: YAG at 532?nm and thereby from closed and open Z-scan data, third-order susceptibilities were calculated to be χ⁽³⁾?=?8.826?×?10^?6 esu for LPN and χ⁽³⁾?=?2.552?×?10^?7 esu for TPLPN.     

Mechanistic and kinetics study of the gas phase reactions of methyltrifluoroacetate with OH radical and Cl atom

Theoretical investigations are carried out on the title reactions by means of ab initio and DFT methods. The optimized geometries, frequencies and minimum energy path are obtained at MPWB1K/6-31+G(d,p) level. Single point energy calculations are performed at MP2 and QCISD(T) levels of theory. Energetics were further refined by calculating the energy of the species with a high level G2(MP2) method. The rate constant of the two reactions are calculated at 298?K and 1?atm using Canonical Transition State Theory (CTST) utilizing the ab initio data obtained during the present study. The rate constant values are found to be 5.5?×?10^?14 and 5.9?×?10^?14?cm³ molecule^?1 s^?1, respectively which are in good agreement with the experimental data.     

Quantum effects in radiation on short bunches

The radiation caused by particles of one bunch in the collective electromagnetic field of the short oncoming bunch is studied. Quantum effects are calculated for the spectrum of radiated photons. Using this spectrum, the dependence of the relative energy loss δ on a quantum parameter K is discussed. It is shown that the behaviour of δ changes considerably with the increase of that parameter. In the classical regime (K ? 1) the energy loss is proportional to the incoming particle energy, while in the extreme quantum regime (K ? 1) the energy loss becomes a constant. The coherent e⁺e^? pair production for γe colliders as cross-channel to CBS is considered.     

Frequency (field) dependent NMR relaxation rate in the interrupted metallic strand model

We calculate the nuclear magnetic resonance rate T^?1₁ arising from the electron-nuclear hyperfine contact interaction, within the interrupted metallic strand model. The electron levels are assumed to have an energy half width Γ and a mean spacing Δ₀ and it is assumed that all segments have the same nuclear spin temperature. In the limit Γ ? Δ₀, T^?1₁ has nearly the same behaviour for kT ? Δ₀ and kT?Δ₀. It is proportional to temperature but has a Lorentzian magnetic field dependence with halfwidth H= Γ/μ_B. At low fields it is enhanced over the value for a normal metal by the factor Δ₀/Γ.This anomalous behaviour arises from the suppression of electron spin flip processes by a magnetic field and should always occur when electronic states are localised, that is when there is a locally discrete electron energy spectrum. Therefore it may be relevant not only to certain linear chain conductors but to other cases of electron localisation.The present model provides an additional possible source of frequency dependence of T₁ in linear chain materials. In certain materials especially those containing defects, it may be more appropriate than the currently accepted mechanism which involves electron spin diffusion in one dimension.     

Spectroscopic Study on the Effect of Imidazophenazine Tethered to 5′-End of Pentadecathymidilate on Stability of Poly(dA)·(dT)15 Duplex

The effect of imidazo[4,5-d]phenazine (Pzn) attached to the 5^′-end of (dT)₁₅ oligonucleotide via a flexible linker on the thermal stability of poly(dA)·(dT)₁₅ duplex was studied in aqueous buffered solution containing 0.1 М NaCl at the equimolar ratio of adenine and thymine bases (100?μM each) using spectroscopic techniques. Duplex formation was investigated by measuring UV absorption and fluorescence melting curves for the Pzn-modified system. Tethered phenazine derivative enhances the thermostability of poly(dA)·(dT)₁₅ duplex increasing the helix–to–coil transition temperature by 4.5?°С due to an intercalation of the dye chromophore between AT-base pairs. The thermodynamic parameters of the transition for non-modified and modified systems were estimated using “all–or–none” model. The modification of the (dT)₁₅ results in a decrease in the transition enthalpy, however, the observed gain in the Gibbs free energy of complex formation, ΔG, is provided with the corresponding decrease in entropy change. The increase of ΔG value at 37?°C in consequence of (dT)₁₅ modification was found to be equal to 1.3?kcal/mol per oligonucleotide strand.     

Equilibrium vacancy concentration measurements on aluminum

Thermal expansion on high purity aluminum has been measured to study defects in thermal equilibrium by the (ΔL/L ₀?Δa/a ₀) method. Measurements of the changes in macroscopic length ΔL and lattice parameter Δa were made from room temperature to 637° C. Length changes were measured by a laser interferometer and lattice parameter changes by a X-ray diffractometer technique on the same crystal at identical temperatures. At temperatures above 400° C ΔL/L ₀ becomes greater than Δa/a ₀, indicating the generation of a noticeable amount of new lattice sites due to vacancy formation. Extrapolation gives a vacancy concentration ΔN/N ₀=9.8·10^?4 at the melting point (660° C). The experimental findings can be explained by assuming formation of monovacancies and divacancies. Values for the enthalpy and entropy of formation for mono- and divacancies are given.     

Variations of microhardness with solidification parameters and electrical resistivity with temperature for Al-Cu-Ag eutectic alloy

Al-Cu-Ag eutectic alloy was directionally solidified upwards with different growth rates (1.83-498.25 μm/s) at a constant temperature gradient (8.79 K/mm) and with different temperature gradients (3.99-8.79 K/mm) at a constant growth rate (8.30 μm/s) by using a Bridgman type directional solidification apparatus. The dependence of microhardness (HV) on the growth rate (V), temperature gradient (G) and microstructure parameter (λ) were found to be HV = k₁ V^0.10, HV = k₂ G^0.13 and HV = k₃ λ^−0.22, respectively. The electrical resistivity of the Al-Cu-Ag eutectic cast alloy increases linearly with the temperature in the range of 300-780 K. The enthalpy of fusion and specific heat change during melting for same alloy were also determined to be 223.8 J/g, and 0.433 J/g K, respectively by a differential scanning calorimeter from heating curve during the transformation from eutectic solid to eutectic liquid.     

Adsorption Kinetics and Binding Studies of Protein Quantum Dots Interaction: A Spectroscopic Approach

Protein Quantum dots interaction is crucial to investigate for better understanding of the biological interactions of QDs. Here in, the model protein Bovine serum albumin (BSA) was used to evaluate the process of protein QDs interaction and adsorption on QDs surface. The modified Stern-Volmer quenching constant (K_a), number of binding sites (n) at different temperatures (298 308 and 318 K?±?1) and corresponding thermodynamic parameters (ΔG?<?0, ΔH?<?0, and ΔS?>?0) were calculated. The quenching constant (K_s) and number of binding sites (n) is found to be inversely proportional to temperature. It signified that static quenching mechanism is dominant over dynamic quenching. The standard free energy change (ΔG?<?0) implies that the binding process is spontaneous, while the enthalpy change (ΔH?<?0) suggest that the binding of QDs to BSA is an enthalpy-driven process. The standard entropy change (ΔS?>?0) suggest that hydrophobic force played a pivotal role in the interaction process. The adsorption process were assessed and evaluated by pseudofirst-order, pseudosecond-order kinetic model, and intraparticle diffusion model.     

Calculated stark widths of oxygen ion lines

Calculations have been performed on the electron impact broadening of isolated lines from singly-ionized and doubly-ionized oxygen emitted from a plasma of electron density 10¹⁷ cm^-3 and temperature about 2 eV. These have been compared with results of measurements performed by Plati?a, Popovi?, and Konjevi? on a plasma produced by a low pressure pulsed arc. Good overall agreement has been obtained for both ionization stages, which we interpret as strong support for a recently derived expression for the effective Gaunt factor in line broadening calculations. This in turn indicates the important role that the curvature of the perturber trajectory plays in the broadening process, and that by proper allowance for this effect, classical path calculations of the isolated ion line widths can be extended to spectra of the multiply-charged ions. Some ambiguity still remains, however, as to the proper method of extrapolation of the effective Gaunt factors below threshold energies in the classical path calculation of the elastic contribution to the broadening. The present comparison appears to indicate that for the higher ionization stages, extrapolation of ? as a constant equal to its threshold value, is satisfactory.     

Temperature dependence of the Raman bandwidths and intensities of a lattice mode near the tricritical and second order phase transitions in NH4Cl

We calculate here the temperature dependence of the damping constant using the expressions derived from the Matsushita's theory and the temperature dependence of the order parameter from the molecular field theory for the tricritical (1.5?kbar) and second order (2.8?kbar) phase transitions in NH₄Cl. Our calculations are performed for the ν ₅ (174?cm^?1) Raman mode of NH₄Cl for the pressures studied. Predictions for the damping constant are in good agreement with our observed Raman bandwidths of this lattice mode for both pressures. The Raman intensities calculated from the molecular field theory by means of the order parameter are also in good agreement with our observed Raman intensities of the ν ₅ (174?cm^?1) mode for both tricritical (1.5?kbar) and second order (2.8?kbar) phase transitions in NH₄Cl. In this study our observed Raman intensities of this lattice mode are analysed using a power-law formula with the critical exponent β for the order parameter at those two pressures considered in NH₄Cl. From our analysis, the value of β?=?0.5 is obtained as the mean field value.     

EFFECTS OF FREE STREAM VELOCITY ON TURBULENT NATURAL CONVECTION FLOW OVER A VERTICAL FORWARD-FACING STEP

Measurements of heat transfer and fluid flow of turbulent boundary-layer air flow in natural and mixed convection over an isothermal two-dimensional, vertical forward-facing step are reported. The upstream and downstream walls and the step itself were heated to a uniform and constant temperature. Air velocity and temperature distributions and their turbulent fluctuations are measured simultaneously using a two-component laser-Doppler velocimeter (LDV) and a cold wire anemometer, respectively. The present study treats buoyancy-dominated mixed convection over a vertical forward-facing step and examines the effect of a small free stream velocity on turbulent natural convection. The experiment was carried out for a step height of 22 mm, for a range of free stream air velocities 0 m/s ? u_∞ ? 0.55 m/s (corresponding to a range of Reynolds numbers of 0 ? Re\abinf{s} ? 712), and a temperature difference, ΔT, of 30°C between the heated walls and the free stream air (corresponding to a local Grashof number Gr_xi = 6.45 × 10¹⁰). It was found that the reattachment length increases while the heat transfer rate from the downstream heated wall decreases as the small free stream velocity increases.     

Computational study on mechanisms and pathways of the atmospheric NH2 + IO reaction

ABSTRACT

The potential-energy surfaces of the amino radical (NH₂) with IO reaction have been studied at the CCSD(T)/cc-pVTZ//MP2/6-311++G(d,p) level. Two kinds of pathways are revealed, namely H-abstraction and addition/elimination. Rice–Ramsperger–Kassel–Marcus theory and transition state theory are employed to calculate the overall and individual rate constants over a wide range of temperatures and pressures. It is predicted that, at atmospheric pressure with N2 as bath gas, the formation of P1 (HI?+?HNO) is the dominant pathways at 200–700?K, while the direct H-abstraction leading to P3 (³NH?+?HOI) takes over the reaction at a temperature above 700?K. At the high-pressure limit, IM1 [IONH₂] formed by collisional stabilisation is dominant at 200–700?K; the direct H-abstraction resulting in P3 (³NH?+?HOI) plays an important role at higher temperatures. However, the total rate constants are independence on the pressure; however, the individual rate constants are sensitive to pressure. The atmospheric lifetime of NH₂ in IO is around one week. TD-DFT computations imply that IM1 [IONH₂], IM1A [IONH₂′], IM2 [IN(H₂)O], IM3 [OINH₂], IM4 [HOINH], tra-IM5 [tra-HON(H)I] and cis-IM5 [cis-HON(H)I] will photolyze under the sunlight.     

Pressure dependence of the superconducting transition temperature of a (Mo0.6Ru0.4)86B14 metallic glass

We have studied the pressure dependence of the superconducting transition temperature of amorphous (Mo_0.6Ru_0.4)₈₆B₁₄ for hydrostatic pressures up to P ～ 9 kbar. The transition temperature T_c decreases with pressure at a rate dT_c/dP=-(9±1) mK kbar^-1. We estimate the Grüneisen parameter and the volume dependence of the electron-phonon coupling constant.