Analysis of Spontaneous Electrochemical Oscillations by the Wavelet Transformation Method

A new way of analyzing current oscillations that accompany anodic metal dissolution is presented. A wavelet transformation is used for separation and spectral analysis of singular courses—elementary components of electrochemical oscillation recordings. A method of obtaining oscillation energy distribution analogous to the spectral power density function is presented. It is shown that the chaotic component (Shil'nikov chaos) can be separated from the deterministic component of the described process.     

Dynamical theory of proton tunneling transfer rates in solution: general formulation

A general dynamical theory is presented for the rate constant of weak coupling, nonadiabatic proton-tunneling reactions in solution. The theory incorporates the critical role of the solvent and the vibration of the separation of the heavy particles between which the proton transfers, including their dynamics. The formulation which allows the computation of the quantum rate constant k via classical molecular dynamics simulation techniques is presented, as are a number of approximate analytic results for k in a variety of different important regimes. The frequent appearance of (nearly) classical Arrhenius behavior for k — even though the intrinsic reactive event is quantum proton tunneling — is discussed, together with the solvent and vibrational contributions to the apparent activation energy. In certain weak solvation limits, however, non-Arrhenius behavior for k is found and is related to vibrational Franck-Condon features in the reaction.     

Hydrodynamical interaction of two emulsion droplets at small separations

The fluid's motion inside emulsion droplets is analysed when they mutually approach along their common axis and a thin liquid film is formed outside. A qualitative flow pattern is presented. Two particular cases are treated — a creeping motion and a boundary layer flow inside the droplets. Estimates are made for the tangential velocity at the droplet/film interface, for the drag force and for the energy dissipated in the respective phases.     

On the calculations of the variational correlation energy using Møller—Plesset first-order wavefunctions

A method is developed, based on first-order symmetry-adapted pair functions obtained within the framework of the Rayleigh—Schrödinger Hartree—Fock perturbation theory, for obtaining a variational upper bound to the correlation energy in the form of pair increments. The correlation-energy functional obtained is written in terms of second- and third-order energy increments of Møller—Plesset perturbation theory. Application of the procedure to the ground states of the Ne-like systems yields energies of greater accuracy than those obtained from CI calculations using very extensive sets of singly and doubly excited configurations. Our pair energies and the total correlation energy obtained for Zn²⁺ represent the most accurate variational results reported so far for atomic systems containing 3d-electrons.     

Efficiency calibration of germanium detectors with internal standards

A simple experimental method for the efficiency calibration of germanium detectors especially for environmental samples is presented, using only the natural radionuclides in the sample. The method is based on the fact that for the energy range above 300 keV the full-energy-peak efficiency of a Ge detector can be described in a first order approximation by a linear interpolation curve in the log-log display with errors lying normally under 5%. Photons with different energies which are emitted from one radionuclide yield count rates which are correlated to the corresponding efficiencies. From this correlation one coefficient of the interpolation curve — a first order polynomial — can be calculated. The second coefficient can be obtained by the count rate of⁴⁰K, resulting from KCl, which is mixed homogeneously with the sample. Expecially for environmental samples with large volumes, this method is very useful, because it takes into account the self-absorption of photons in the sample.     

Microemulsions: Effect of alkyl chain length of alcohol and alkane

In microemulsions consisting of four components, i.e. detergent — water — oil — cosurfactant, the free energy of transfer from the continuous oil phase to the interfacial region for the cosurfactant is reported. From the effect of temperature on the free energy, the entropy and the enthalpy values are also reported. The effect of chain length of the alcohol (cosurfactant) is also described. It is further shown, that if the oil phase consists of hexadecane, then the free energy changes as a linear function of the number of carbon atoms in the cosurfactant. On the other hand, if the oil phase is benzene, the cosurfactant chain length has very little effect. These data are analyzed with respect to the microemulsion structure and stability.     

Quantum calculations on the adsorption of halide ions on the noble metals

The interaction of halide ions with the three noble metals has been investigated using the B3LYP density functional method and the cluster model approximation. The results of calculations for the M—X⁻ and M₁₂—X⁻ (M = Cu, Ag, Au; X = F, Cl, Br, I) systems are presented. At the (100) surface, modeled in the present work by the M₁₂ cluster, all halide ions have been found to adsorb preferentially at the hollow site, followed by the bridge and by the top positions. The adsorption energy has been found to decrease when going from fluoride to iodide in both atom—ion and cluster—ion cases. The opposite trend is observed for the estimates of the charge transfer from the ions to the surface. When different metals are compared, the M₁₂—X⁻ interaction energies decrease in the order Au > Ag > Cu, but for the smaller ions some deviations from this line do appear. The relative values of the calculated harmonic vibrational frequencies do agree with those found experimentally, but their magnitude is much smaller as a result of the effect of the lower surface coverage.     

Theoretical study on the hydrogen migration reactions in ground state vinyl fluoride: Basis set and correlation energy effects

We performed ab initio molecular orbital (MO) calculations using Hartree—Fock SCF, and second- and fourth-order Møller—Plesset perturbation theory for hydrogen migration reactions on the singlet vinyl fluoride potential energy surface. We used different basis sets and polarization functions to obtain the stationary point geometries and activation barriers. Basis set and the polarization function extension have small effects, while the correlation energy evaluation leads to new conclusions for one of the studied reactions: the product singlet CHCH₂F is not a true local minimum on the potential energy surface.     

Calculated vibrational spectra of weak hydrogen bonds

Potential energy and dipole moment surfaces for the H-bond SH... S in the dimeric methanethiol have been calculated by the SCF-MO-LCGO method, and the vibrational spectrum — transition frequencies and IR absorption intensities at 20 °K — computed. This spectrum is compared with that of the monomeric species and with experimental results. The resulting dimerization energy is 1.4 kcal/mole.     

Arbitrary l‐wave bound states of the Schrödinger equation for the hyperbolical molecular potential

Within the framework of supersymmetric quantum mechanics method, we study by an algebraic method the arbitrary l‐wave bound states of the Schrödinger equation for the hyperbolical molecular potential by a proper approximation to nonlinear centrifugal term. The explicitly analytical formula of energy levels is derived, and the corresponding bound state wave functions are presented. The function analysis method is used to rederive the same energy levels of the quantum system under consideration to check the validity of this algebraic method. In addition, it is shown from numerical results of energy levels that above certain α parameter depending on the choices of potential parameters V₁ and V₂ the hyperbolical molecular potential cannot trap a particle as it becomes weaker and the energy level starts to turn positive when the potential parameter α becomes larger. © 2014 Wiley Periodicals, Inc.     

Effect of the fifth coordination site on the spin states of bis(benzoylacetylacetanato)bispyridinedicopper(II) complex

The spin and charge excitation gap and spin density have been calculated for bis(benzoylacetylacetanato)bispyridinedicopper(II) using a valence bond basis and model Hamiltonian based on the Pariser—Parr—Pople (PPP) approximation. The singlet—triplet energy gap depends upon the exchange interaction (K_oo) of the bridging oxygen atom. The results of this 12-orbital, 18-electron system are compared with those of a 10-orbital, 14-electron system, viz. bis(benzoylacetylacetanato)dicopper(II), the latter without axial ligation. Changing the nitrogen to oxygen in the fifth coordination site does not seem to affect the singlet—triplet energy gap and spin and charge density on the copper(II) atoms. The results indicate that K_oo, which is sensitive to geometry, plays a decisive role in determining the excitation gap.     

Substitution effect on the intermolecular halogen and hydrogen bonds of the σ‐bonded fluorinated pyridine···XY/HX complexes (XY = F2, Cl2, ClF; HX = HF,HCl)

Optimal structures, electronic and thermodynamic properties of the title complexes are presented. The stability of the hydrogen bonded systems is enhanced by the increasing dipole moments whereas in the halogen bonded systems it is also affected by the atom size in the diatomics. The consecutive addition of fluorine atoms to the pyridine moiety results in the decrease of the interaction energy for both types of the investigated bonds. The substitution on the meta sites in pyridine leads to more stable complexes than the substitution in the ortho position. The role of substitution on electric polarization and electrostatic forces is estimated by the symmetry‐adapted perturbation theory energy decomposition. The predicted Gibbs free energies of the complexes of mono fluorinated pyridines with HCl, HF, and ClF are from ?12 to ?22 kJ mol^?1 at 200 K. The possible experimental identification of the complexes with respect to the vibrational modes is discussed. © 2014 Wiley Periodicals, Inc.     

Resolutions of the Coulomb operator: VIII. Parallel implementation using the modern programming language X10

Use of the modern parallel programming language X10 for computing long‐range Coulomb and exchange interactions is presented. By using X10, a partitioned global address space language with support for task parallelism and the explicit representation of data locality, the resolution of the Ewald operator can be parallelized in a straightforward manner including use of both intranode and internode parallelism. We evaluate four different schemes for dynamic load balancing of integral calculation using X10's work stealing runtime, and report performance results for long‐range HF energy calculation of large molecule/high quality basis running on up to 1024 cores of a high performance cluster machine. © 2014 Wiley Periodicals, Inc.     

The READY program: Building a global potential energy surface and reactive dynamic simulations for the hydrogen combustion

READY (REActive DYnamics) is a program for studying reactive dynamic systems using a global potential energy surface (PES) built from previously existing PESs corresponding to each of the most important elementary reactions present in the system. We present an application to the combustion dynamics of a mixture of hydrogen and oxygen using accurate PESs for all the systems involving up to four oxygen and hydrogen atoms. Results at the temperature of 4000 K and pressure of 2 atm are presented and compared with model based on rate constants. Drawbacks and advantages of this approach are discussed and future directions of research are pointed out. © 2014 Wiley Periodicals, Inc.     

Looking for some free energy? Call JEFREE (…)

In this communication, we present the Jarzynski's Equality FREe Energy (JEFREE) library, an efficient and easy‐to‐use C++ library targeted to the calculation of the free energy profile along a selected generalized coordinate of a system, within the framework of the nonequilibrium steered transformations as introduced by Jarzynski [Phys. Rev. E, 1997, 56, 5018]. JEFREE can be readily integrated into any code, since both C and FORTRAN wrappers have been developed, and easily customizable by a user thanks to the object‐oriented programming paradigm offered by the C++ language. Also, JEFREE implements the novel idea of making a total “morphing” of the system energy landscape before initiating the proper steering stage. This proves to be an efficient mean to overtake the problematic sampling of the initial equilibrium state when the number of degrees of freedom is high and the landscape owns many local minima separated by large energy barriers. The calculation of the free energy profile for the rotation along torsion angles in alkyl chains is presented as an example of application of our tool. © 2014 Wiley Periodicals, Inc.     

On the problem of directed signal transmission and energy transfer in molecular systems

A new physical interpretation of the mechanism of directed energy transfer and signal transmission in molecular systems along one-dimensional chains capable of successive isomerization is proposed. The photoacceptor—transmitting chain—reaction center system is considered as a model. Conditions under which the directed energy transfer occurs from the photoacceptor to the reaction center along the chain are analyzed. The time of signal transmission depends on the chain length, and the transmission coefficient is mainly determined by the characteristics of the initial and final elements in the whole system.     

Hydrogen bonding of water, hydrogen sulphide and related acceptors with electron donors

Properties of hydrogen bonds formed by 1:1 interaction of H₂O with oxygen, nitrogen, sulphur and other electron donors have been evaluated by extended Hückel and CNDO methods and the results are discussed in relation to the experimental data. A detailed analysis of the variation of the dissociation energies and charge densities with bond distances is presented for the amine-water system. 1:2 complexes of water with donors are found to contain weaker hydrogen bonds than 1:1 complexes. Results of molecular orbital calculations on the hydrogen bonding of H₂S and CH₃SH with some donors are presented. The theoretical value of hydrogen bond dissociation energy varies linearly with the overlap population, and stretching force constant of the hydrogen bond as well as with the experimental O—H frequency shift.     

Free energy and chemical potentials of regular multicomponent solution with molecules of different size

Equations are proposed for the free energy and chemical potentials of regular multicomponent solutions containing molecules of different sizes. The use of the equations for calculations on the three-component system, methyl ethyl ketone—heptane—toluene, gives results which agree well with experiment.     

On the linearity of the energy of activation in theEyring theory of kinetics

Summary A result obtained earlier implies that — if theEyring theory is correct — the energy of the transition state is less thanU+E _a whereU is the sum of the internal energies of the chemical reactants andE _a is the energy of activation. The energy of the transition state for the forward reaction is not equal to that of the inverse reaction; it varies linearly with the temperature.

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Zur Linearität der Aktivierungsenergie in derEyringschen Theorie

Zusammenfassung Aus einem früher erhaltenen Ergebnis folgt, daß — Richtigkeit derEyring-Theorie vorausgesetzt — die Energie des Übergangszustands geringer ist alsU+E _a (U: Summe der inneren Energien der Reaktanden;E _a: Aktivierungsenergie). Die Energie des Übergangszustands ist für Hin- und Rückreaktion unterschiedlich und hängt linear von der Temperatur ab.