新型BrФnsted酸性离子液体的合成与表征

制备了五种对水稳定性好、带-SO3H官能团的磺酸类BrФnsted酸离子液体,用核磁共振(NMR)、红外光谱(IR)、电喷雾质谱(ESI-MS)、热重分析(TG)等表征手段对制备的离子液体进行了表征。结果表明,制备的离子液体与预期设计的结构一致,离子液体纯度大于95%;热重分析发现离子液体具有高的热稳定性和较宽的液态范围,其分解温度均高于300℃;五种离子液体均存在四种离子存在形式,H 可以单独以离子形式存在,并不是通常所认为的仅有两种离子存在形式。另外,研究了离子液体在常用溶剂中的溶解性,发现制备的离子液体易溶于水、甲醇,不溶于乙醚、甲苯和乙酸乙酯。     

E.S.R. spectrum of 3,5-lutidine anion and comments on nitrogen hyperfine couplings

The E.S.R. spectrum of the 3,5-lutidine anion has been observed. The methyl groups prevent the dimerization which occurs for pyridine. From the observed splitting constants and those of the pyrazine negative ion an estimate is made of the relative contribution to the nitrogen hyperfine splitting of the π-orbital spin densities on the nitrogen atom and on the adjacent carbon atoms.     

A comment on classical rainbow angles for atom-atom scattering

The dependence of the rainbow angle on the depth of the potential well, the equilibrium distance, andthe force constant of the potential are discussed for several potential functions.     

Dynamics of the 18O + 16O2(υ=0) exchange reaction on a new potential energy surface for ground-state ozone

A quasiclassical trajectory study of the thermoneutral isotopic oxygen exchange reaction was made using a recently reported potential energy surface for the ground state of ozone. The calculated macroscopic rate constants show an improvement over the previous quasiclassical results when compared with the experimental values.     

A theoretical study of the non-adiabatic charge transfer process Ar2+ (3 P) + He(1 S) → Ar+(2 P) + He+(2 S)

CI calculation with a large basis have been used to calculate the two lowest ³Π adiabatic potential energy curves for the title reaction. These potentials have been transformed to diabatic potentials by employing a recipe based on the CI coefficients. Quantum mechanical close coupling calculations in the diabatic basis have produced total and differential cross sections which are in good agreement with experimental data. Full quantum mechanical and Landau-Zener calculations of the total cross section are in fair agreement with recent experimental measures and by small changes to the diabatic potentials can be brought into essentially exact agreement.     

Complete Cl calculations on the ground state of HeH

Complete Cl calculations on the van der Waals molecule HeH with a large Gaussian basis set give the depth of the potential well as c = 0.50 meV and a minimum at R_m = 3.64 Å. An analytical function has been fitted to the ab initio points and to the best estimates of the dispersion energy coefficients. One further parameter in the potential has been chosen to reproduce the HeH scattering cross section.     

Molecular orbitals and the virial theorem

It is shown that for H₂ ⁺ and H₂ an atomic orbital exponent chosen from the condition = - E _obs. gives calculated total energies which are insignificantly different from those obtained using a obtained through a variational treatment. A scheme is proposed in which the atomic orbital exponents of -electron molecular orbitals are taken to be a function of the orbital energies, such that these molecular orbitals qualitatively satisfy the virial theorem.

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Zesummenfassung Es wird gezeigt, daß für H₂ ⁺ und H₂ ein Atomorbital-Exponent , der entsprechend der Bedingung = - E _obs. gewählt wurde, zu Gesamtenergien führt, die nur unwesentlich von jenen abweichen, die man nach der Variations-Methode erhält. Es wird ein Verfahren vorgeschlagen, in welchem der Exponent der Atomorbitale eines -Elektronensystems als Funktion der Orbitalenergien angesetzt wird, so daß diese Orbitale dem Virial Theorem qualitativ genügen.

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Resume On montre que l'exposant que l'on choisit pour les orbitales atomiques de H₂ ⁺ et H₂ en se servant de la condition = - E _obs. diffère d'une façon insignifiante de celui calculé par la méthode variationelle. On propose un procédé dans lequel les exposants des orbitales atomiques de systèmes n sont fonction de l'énergie des orbitales moléculaires de manière que le théorème du viriel est qualitativement satisfait.

     

Fragmentation and reactions of two isomeric O-alkyl S-(2-dialkylamino)ethyl methylphosphonothiolates studied by electrospray ionization/ion trap mass spectrometry

An initial investigation into the electrospray ionization ion trap mass spectrometry (ESI/ITMS) of simple organophosphorus compounds [1] demonstrated that detailed structural information could be obtained by sequential fragmentation of the ions using collision induced dissociation (CID). Several novel fragmentations/rearrangements were observed and it was apparent that the full potential of this approach could not be exploited until a more detailed understanding of the ion fragmentations was obtained. Such an understanding will only result from a detailed study of a wide range of compounds. The present paper describes the investigation of two isomeric organophosphates of particular relevance to chemical warfare convention (CWC) considerations.     

Comparison of the effects of ionization mechanism, analyte concentration, and ion “cool-times” on the internal energies of peptide ions produced by electrospray and atmospheric pressure matrix-assisted laser desorption ionization

The propensities of a series of peptide ions produced by both electrospray and atmospheric pressure matrix assisted laser desorption ionization (AP-MALDI) to fragment in an ion trap mass spectrometer under various conditions were studied in detail by measuring the extent of fragmentation of precursor ions by collision induced dissociation (CID) as a function of applied resonance excitation RF voltage. For the most basic peptides, the energy required to fragment MH+ ions generated by electrospray exceeded that required to fragment equivalent AP-MALDI ions under identical instrumental conditions; the reverse was observed for a peptide incorporating no basic residues, while peptides of intermediate basicity showed little difference between the ionization methods. This correlation between peptide basicity and the difference in the energy required to induce fragmentation of MH+ ions generated by AP-MALDI and electrospray is attributed primarily to a trend in the internal energies of the ions generated by AP-MALDI (the greater the difference in gas-phase basicities between the matrix and the analyte the greater the internal energy of the analyte ions produced). Furthermore the internal energies of ions produced by AP-MALDI, but not the equivalent ions formed by electrospray, were observed to decrease with decreasing analyte concentration. We attribute this finding to the cooling effect of endothermic dissociation of analyte ion/matrix molecule clusters following the matrix assisted laser desorption step. Time-resolved analyses (measurement of extent of fragmentation of precursor ions by CID as a function of pre-CID "cool times") revealed that cooling periods in excess of 250 ms were required to achieve internal energy equilibrium through cooling collisions with the helium buffer gas. Furthermore, these analyses demonstrated that, even after these extended cooling times, equivalent ions formed by the two ionization techniques showed different propensities to fragment. We conclude that the two different ionization techniques produce ion populations that may differ in their three-dimensional structure.