Electrostatic potentials of molecules and prediction of the lewis acid-base properties of solvents,part I. General considerations

Summary Electrostatic potentials in the vicinity of isolated molecules of typical nonaqueous solvents were computed in the MNDO approximation. It was found that the calculated dipole moments are in good agreement with experimental values. However, it turned out that in many cases electrostatic interactions of ions with solvent molecules cannot be described in the frame of ion-dipole interactions. Thus, two computable parameters,UN andUP describing short-range electrostatic interactions of a solvent molecule with a cation or an anion of radiusR were proposed. The dependence ofUN andUP uponR is analyzed in the context of ion-solvent interactions.

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Elektrostatische Potentiale von Molekülen und Voraussage von Lewis-Säure-Base-Eigenschaften von Lösungsmitteln, 1. Mitt.: Allgemeine Grundlagen

Zusammenfassung Es wurden die elektrostatischen Potentiale in der Umgebung von isolierten Molekülen typischer nichtwäßriger Lösungsmittel in der MNDO-Näherung berechnet. Die berechneten Dipolmomente waren in guter Übereinstimmung mit den experimentellen Werten. Es wurde jedoch beobachtet, daß in vielen Fällen die elektrostatischen Wechselwirkungen von Ionen mit Lösungsmittelmolekülen nicht im Rahmen von Ionen-Dipol-Wechselwirkungen beschrieben werden können. Dafür wurden zwei berechenbare ParameterUN undUP zur Beschreibung von elektrostatischen Wechselwirkungen im Nahbereich eines Lösungsmittelmoleküls mit einem Kationen- oder AnionenradiusR vorgeschlagen. Die Abhängigkeit vonUN undUP vonR wurde im Zusammenhang von Ionen-Solvens-Wechselwirkungen untersucht.

     

Regularity and other properties of absolutely continuous invariant measures for the quadratic family

In the current paper we study in more detail some properties of the absolutely continuous invariant measures constructed in the course of the proof of Jakobson's Theorem. In particular, we show that the density of the invariant measure is continuous at Misiurewicz points. From this we deduce that the Lyapunov exponent is also continuous at these points (our considerations apply just to the parameters constructed in the proof of Jakobson's Theorem). Other properties, like the positivity of the Lyapunov exponent, uniqueness of the absolutely continuous invariant measure and exactness of the corresponding dynamical system, are also proved.This paper was written during the author's stay at the IAS while supported by NSF grant DMS-860 1978     

Grow-up rate of solutions for a supercritical semilinear diffusion equation

We study solutions of the Cauchy problem for a supercritical semilinear parabolic equation which converge to a singular steady state from below as t→∞. We show that the grow-up rate of such solutions depends on the spatial decay rate of initial data.     

Polysiloxanol condensation and disproportionation in the presence of a superacid

Kinetics studies of the condensation of model hydroxyl-terminated oligosiloxanes, pentamethyldisiloxane-1-ol (MDH) and heptamethyltrisiloxane-1-ol (MD₂H), catalysed by protic complex of tetrakis(pentafluorophenyl)borate in the toluene solution were performed. The dominating reaction was condensation, which was accompanied by disproportionation of oligosiloxanols. Water released in the condensation forms separate dispersed phase, but the phase separation and the presence of water does not affect the rate of the polycondensation. Both processes, condensation and disproportionation, show analogous kinetic laws being first order in silanol and half order in catalyst. They exhibit also similar values of activation parameters. The kinetics are explained by the formation of a reactive protic complex of silanol with borate being in fast preequilibrium with an unreactive complex including two borate molecules and the silanol molecules. The equilibrium lies to the side of the unreactive borate complex.     

Algebraization of Spectral Problems in the Bargmann—Fock Representation

Examples of quasi-exactly solvable hamiltonians in the Bargmann—Fock representation are given. The existence of an invariant subspace is studied as a result of hidden symmetry of the spectral problem.     

Effect of Ga doping on magneto-transport properties in colossal magnetoresistive La0.7Ca0.3Mn1−xGaxO3 (0<x<0.1)

Samples of La_0.7Ca_0.3Mn_1−xGa_xO₃ with x=0, 0.025, 0.05 and 0.10 were prepared by standard solid-state reaction. They were first characterized chemically, including the microstructure. The magnetic properties and various transport properties, i.e. the electrical resistivity, magnetoresistivity (for a field below 8 T), thermoelectric power and thermal conductivity measured each time on the same sample, are reported. The markedly different behaviour of the x=0.1 sample from those with a smaller Ga content, is discussed. The dilution of the Mn³⁺/Mn⁴⁺ interactions with Ga doping considerably reduces the ferromagnetic double exchange interaction within the manganese lattice leading to a decrease of the Curie temperature. The polaron binding energy varies from 224 to 243 meV with increased Ga doping.     

An engine breaking the ΩEP-property

We present a construction which shows that some special continua do not have the nonwandering-eventually-periodic property. The construction applies e.g. to the topologist's sin curve and to the harmonic fan.     

Crystal structure of m-nitrobenzoic anhydride

The title compound (C₁₄H₈N₂O₇,M _r =306.2) crystallizes in the orthorhombic space group Pbca witha=6.962(1).b=24.688(1), andc=15.890(1)Å,V=2731.0 ų,D _x =1.489 g·cm^–3 forZ=8,=0.98 mm^–1,F(000)=1296,T=293 K. FinalR=0.053 for 1873 observed reflections. The structure was solved by direct methods. Approximately planar molecules lie perpendicular to the [100] direction and show partial stacking. The structure is the first example of a symmetric anhydride which does not retain the symmetry in the crystal state. The two independent nitro groups twist out of the ring planes by 10.5 and 14.8°, respectively.     

Comparison theorems for weak splittings of bounded operators

Summary Comparison theorems for weak splittings of bounded operators are presented. These theorems extend the classical comparison theorem for regular splittings of matrices by Varga, the less known result by Wonicki, and the recent results for regular and weak regular splittings of matrices by Neumann and Plemmons, Elsner, and Lanzkron, Rose and Szyld. The hypotheses of the theorems presented here are weaker and the theorems hold for general Banach spaces and rather general cones. Hypotheses are given which provide strict inequalities for the comparisons. It is also shown that the comparison theorem by Alefeld and Volkmann applies exclusively to monotone sequences of iterates and is not equivalent to the comparison of the spectral radius of the iteration operators.This work was supported by the National Science Foundation grants DMS-8807338 and INT-8918502     

On two mean value properties and functional equations associated with them

Summary Motivated by different mean value properties, the functional equationsf(x) – f(y)/x–y=[(x, y)], (i)xf(y) – yf(x)/x–y=[(x, y)] (ii) (x y) are completely solved when, are arithmetic, geometric or harmonic means andx, y elements of proper real intervals. In view of a duality between (i) and (ii), three of the results are consequences of other three.The equation (ii) is also solved when is a (strictly monotonic) quasiarithmetic mean while the real interval contains 0 and when is the arithmetic mean while the domain is a field of characteristic different from 2 and 3. (A result similar to the latter has been proved previously for (i).)