Sur la mesure de sortie du super mouvement brownien

Summary We study some properties of the exit measure of super Brownian motion from a smooth domainD inR ^d . In particular, we give precise estimates for the probability that the exit measure gives a positive mass to a small ball on the boundary. As an application, we compute the Hausdorff dimension of the support of the exit measure. In dimension 2, we prove that the exit measure is absolutely continuous with respect to the Lebesgue measure on the boundary. In connection with Dynkin's work, our results give some information on the behavior of solutions of u=u ² inD, and are related to the characterization of removable singularities at the boundary. As a consequence of our estimates, we give a sufficient condition for the uniqueness of the positive solution of u=u ² inD that tends to on an open subsetO of D and to 0 on the complement in D of the closure ofO. Our proofs use the path-valued process studied in [L2, L3].

     

Iterated function systems and dynamical systems

We study the relationship between measures invariant for a piecewise expanding transformation tau of a compact metric space endowed with a underlying measure and measures invariant for an iterated function system T(tau), generated by inverse branches of tau. The main result says that the tau-invariant absolutely continuous measure &mgr; is also T(tau) invariant if and only if tau is absolutely continuously conjugated with a piecewise linear transformation. Measures of maximal entropy and general equilibrium states are also discussed. (c) 1995 American Institute of Physics.     

Thermodynamic parameters for the transfer of ions from water to propylene carbonate

There are large discrepancies between various recorded values for the free energy of transfer of the alkali metal cations from water to propylene carbonate. Using the known enthalpies of transfer given byKrishnan andfriedman, and the entropy correlation introduced byAbraham, these discrepancies are resolved in favour of the values obtained byCourtot-Coupez et al. and those due (indirectly) toGritzner. This enables, for the first time, a reasonably reliable set of free energies, entropies, and enthalpies of transfer to be constructed.

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Thermodynamische Parameter für die Übertragung von Ionen von Wasser in Propylencarbonat

Zusammenfassung Die verschiedenen veröffentlichten Werte für die freie Enthalpie der Übertragung von Alkalimetallkationen von Wasser in Propylencarbonat zeigen große Unstimmingkeiten. Diese Unstimmigkeiten können zugunsten der Werte vonCourtot-Coupez et al. und der (indirekten) vonGritzner behoben werden, wenn man die bekannten Werte für die Übertragungsenthalpie vonKrishnan undFriedman, und die vonAbraham eingeführte Entropiekorrelation benützt. Es ist nun zum ersten Mal möglich, relativ zuverlässige Werte für die freie Energie, Entropie und Enthalpie auszuarbeiten.

     

1H chemical shifts in NMR. Part 21--prediction of the 1H chemical shifts of molecules containing the ester group: a modelling and ab initio investigation

The 1H NMR spectra of 24 compounds containing the ester group are given and assigned. These data were used to investigate the effect of the ester group on the 1H chemical shifts in these molecules. These effects were analysed using the CHARGE model, which incorporates the electric field, magnetic anisotropy and steric effects of the functional group for long-range protons together with functions for the calculation of the two- and three-bond effects. The effect of the ester electric field was given by considering the partial atomic charges on the three atoms of the ester group. The anisotropy of the carbonyl group was reproduced with an asymmetric magnetic anisotropy acting at the midpoint of the carbonyl bond with values of Deltachi(parl) and Deltachi(perp) of 10.1 x 10(-30) and -17.1 x 10(-30) cm3 molecule(-1). An aromatic ring current (=0.3 times the benzene ring current) was found to be necessary for pyrone but none for maleic anhydride. This result was confirmed by GIAO calculations. The observed 1H chemical shifts in the above compounds were compared with those calculated by CHARGE and the ab initio GIAO method (B3LYP/6-31G**). For the 24 compounds investigated with 150 1H chemical shifts spanning a range of ca 10 ppm, the CHARGE model gave an excellent r.m.s. error (obs - calc) of <0.1 ppm. The GIAO calculations gave a very reasonable r.m.s. error of ca 0.2 ppm although larger deviations of ca 0.5 ppm were observed for protons near to the electronegative atoms. The accurate predictions of the 1H chemical shifts given by the CHARGE model were used in the conformational analysis of the vinyl esters methyl acrylate and methyl crotonate. An illustration of the use of the CHARGE model in the prediction of the 1H spectrum of a complex organic molecule (benzochromen-6-one) is also given.     

Nachweis von Organophosphorinsecticiden durch Gas-Chromatographie-Massenspektrometrie

Zusammenfassung Die Elektronenstoß-Massenspektren (EI-MS) von 49 Organophosphorinsecticiden wurden in Gas-Chromatographie-Massenspektrometrie-Kopplung unter Bedingungen gemessen, die denen in der Rückstandsanalyse entsprechen. Die EI-MS der Vertreter der 4 Substanzklassen Dithiophophorsäureester, Thiono- und Thiolphosphorsäureester und Phosphorsäureester wurden in Gruppen nach Dimethyl- und Diäthylester unterteilt. Für diese 8 Substanzgruppen wurden die 5 Ionenm/e 93, 97, 109,121 und 125 als gruppentypisch erkannt. Mit diesen Fragmenten ist eine Zuordnung der Verbindungen zu den einzelnen Gruppen möglich.Zusätzlich zu den gruppentypischen Ionen wurden für alle 49 Pesticide aus den EI-MS substanztypische Ionen ausgewählt, die eine Identifizierung der einzelnen Organophosphorinsecticide in der Rückstandsanalyse ermöglichen. Die Auswahl der substanztypischen Ionen wird diskutiert unter Betonung der Frage, ob in den EI-MS anderer Phoshorpesticide die gleichen Ionen gefunden werden.Für die eindeutige Identifizierung wird die GC-MS-Kopplung mit Einfach- und Mehrfachmassenregistrierung der ausgewählten Ionen unter Berücksichtigung von Retentionszeit und des Phosphornachweises mit dem Alkaliflammenionisationsdetektor vorgeschlagen.

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Detection of organophosphorus insecticides by gas chromatography/mass spectrometry

Summary The Electron impact mass spectra (EI-MS) of 49 organophosphorus insecticides were measured in gc-ms mode under conditions generally used in residue analysis. The EI-MS of compounds of the 4 substance classes phosphorodithioates, phosphorothionates, phosphorothiolates, and phosphates were further divided into the groups of dimethyl esters and diethyl esters. For these 8 substance groups the 5 ions atm/e 93, 97, 109, 121, and 125 were found to be indicative for the corresponding structure. With these 5 fragments individual compounds can be classified into the different structure groups.In addition, to these group typical ions for each of the 49 pesticides a series of ions was selected which are characteristic for each individual pesticide allowing an unequivocal identification of these compounds in residue analysis. The choice of the ions characteristic for individual pesticides is discussed accentuating the question whether the same ions may be found in the EI-MS of other organophosphorus pesticides.As an identification procedure gc-ms with single ion detection and multiple ion detection in combination with the retention time and the positive response of the alkaliflame detector is proposed.

Photokopien der in Tabelle 1 in der Spalte Ref. mit einem + versehenen Massenspektren können vom Autor angefordert werden.     

Hydrogen bond structural group constants

The ability of functional groups to act as hydrogen bond acids and bases can be obtained from either equilibrium constants for 1:1 hydrogen bonding or overall hydrogen bond constants. Either method leads to structural constants for hydrogen bonding that in some way are analogous to substituent constants. Extensive lists of these functional group constants are reported. It is shown that those derived from overall hydrogen bond constants are the more useful in analyses of physicochemical and biochemical properties.     

Comparison of CIS- and EOM-CCSD-calculated adiabatic excited-state structures. Changes in charge density on going to adiabatic excited states

The CIS and EOM-CCSD adiabatic geometries for the first excited states of a set of small molecules (C2H4, C2H2, H2C=O, H2C=S, CS2, CO2, SO2, NO2) have been calculated using the 6-311++G** basis set to see if the former geometries can be good starting points for optimizations at the latter theoretical level. With most of the molecules, there is fairly good agreement between the results from the two methods, and EOM-CCSD gives good agreement with the available experimental data. A detailed discussion of the lowest-lying singlet excited states in CO2 and CS2 is presented, highlighting the pronounced differences in electronic character and equilibrium structure displayed by these isovalent species. The origins of the structural distortions that are frequently found for the adiabatic excited states are examined with the aid of deformation density plots and the electron localization function (ELF).