Recent results in muonium solution kinetics

Using Muonium Spin Rotation (MSR) techniques the aqueous solution kinetics of several muonium addition reactions and spin conversion interactions have been studied. The addition reactions show both diffusion and activation-controlled reaction rates with isotope effects between 1 and 3 for diffusion-control and between 7 and 31 for activation-control reactions. Barrier energies are typically 15 kJ/mole and 30 kJ/mole, respectively, for these processes in water. Spin-conversion interactions involving Ni_(aq ⁺² and Ni(cyclam)⁺² complexes showed that spin-conversion of triplet Mu by a paramagnetic solute occurs at or near the diffusion-controlled limit while the chemical reaction with the diamagnetic configuration of Ni(cyclam)⁺² occured some 100 times slower at k_M 5×10⁸M^–1s^–1.     

Muon charge exchange and muonium spin exchange in gases

The spin dynamics of the positive muon undergoing cyclic charge exchange (μ⁺⇌Mu) while it is slowing down is compared with that in the case of repeated muonium spin exchange after thermalization. The expectation value of the spin polarization at timet aftern spin exchange collisions (att ₁,t ₂, ...,t _n ) are calculated explicitly from time dependent wave functions, and the quantity is averaged over the statistical distribution of the times of collisions and over all possible numbers of collisions betweent=0 and the observation timet. This result is complementary and equivalent to the conventional density matrix formalism, but offers an insight into the roles of spin flip and spin non-flip processes. The neutral fraction during slowing down is also discussed.     

Comments on the stability of charge states and locations for hydrogen and muonium in semiconductors

This paper brings together some current concepts concerning hydrogen states in semiconductors (illustrated with reference to silicon but quite generally applicable) and highlight certain findings of recent quantum electronic structure calculations for defect centres involving hydrogen and its isotopes. As regards muonium, the situation which held in the early μSR literature [1] is entirely reversed: the location and structure of Mu^* are now well established [2], whereas the precise location and the nature of the metastability of Mu′ have become open questions! In fact, neither state is stable in the presence of other electrically active impurities, which undoubtedly accounts for the difficulty in detecting paramagnetic protium. The implications for the interpretation of existing data, and for various possible future experiments, are examined.     

Rate constants for the reaction of muonium with aromatic compounds

Rate constants for the reaction of muonium with benzene in water, methanol and n-hexane and for the reaction of muonium with p-difluorobenzene, anilin, hexafluorobenzene and styrene are reported. All rate constants are below the calculated diffusion controlled limit. The activation energy for the reaction of muonium with benzene in n-hexane is very small, indicating the possibility of tunnelling by muonium.     

Interaction of muonium with molecules of biological interest in water solution

Muonium's reaction constants with DNA and its constituents in water solutions are reported and compared with the available data for hydrogen. The low frequency spectrum of the resulting muonic radicals in low magnetic fields is recognized.This work was supported by Consiglio Nazionale delle Ricerche, contract n^o 75.00862.02 and by CERN, Experimental Physycs Division. Data analysis performed at CINECA computation facilities.     

Electrodynamics of effective charge

A portion of the charge induced in an isotropic plasma by an injected charged particle is shown to combine with the particle to form a charged quasi-particle, the effective charge, that is different from the conventional “dressed” charge. The remainder of the induced charge is found in a wake behind the effective charge. Properties of effective charge are described, and the application of this concept to coherent ion acceleration and stopping power is discussed.     

Determination of the effective nuclear charge from EPR data using a modified crystal-field theory

We propose a scheme for determining the effective nuclear charge Z _ef^CF of a 3d ion placed in a crystal field of arbitrary symmetry. As an example, we consider the Co²⁺ ion in a matrix MCO₃ (M = Ca, Cd). We show that the effective nuclear charge Z _ef^CF correlates with a change in the degree of the bond covalence.     

Synthesis of some new triamide derivatives via Ugi five-component reaction in aqueous solution

Triamide derivatives have been synthesized in good yields in a novel, one-pot, five-component, and efficient process by the reaction of Z-oxazolone, water, primary amines, aldehydes, isocyanides, in the presence of catalytic amount of KAl(SO₄)₂·12H₂O (alum) as a non-toxic, reusable, inexpensive, and easily available reagent via Ugi reaction in aqueous solution.     

LUMINOL-氢氧化物水溶液的荧光及其声激发

本文提出和初步研究了声致荧光方法,测出了三种luminol-氢氧化物水溶液的声致荧光光谱,并对比了它们的光致荧光光谱。结果表明,这类物质的荧光可以由声波激发获得,而且声激发和光激发的荧光波长都在luminol水溶液的光致荧光的发射波长370—750um之间,属于可见光和近紫外光;相对于光致荧光而言,声激发的这三种溶液的最大荧光峰呈现大致10—20um的红移。     

Determination of the effective nuclear charge for free ions of transition metals from experimental spectra

The refined set of values of the effective nuclear charge (\(\bar Z_{ef} \)) and the set of one-electron spin-orbital constants (ξ _3d ^teor ) are obtained for ions of transition metals with the help of a semiempirical method of calculation of the spectrum of free ions with allowance for the spin-orbital interaction. The effective nuclear charge, which is a variable theoretical parameter, was determined from a comparison of theoretically calculated ion absorption spectra with experimental ones. The form of the potential for the calculation of the spin-orbital constant was chosen such that the calculated value ξ _3d ^teor would coincide with the experimental one ξ _3d ^exp . The calculated set of values \(\bar Z_{ef} \), ξ _3d ^teor } can be used in semiempirical calculations of energy levels of 3d ions (ions with an incomplete 3d shell).     

Kinetic investigation on carbamate formation from the reaction of carbon dioxide with amino acids in homogeneous aqueous solution

The kinetics of carbamate formation from the reaction of carbon dioxide with α‐amino acids in D₂O was first investigated by means of nuclear magnetic resonance spectroscopy. Potassium carbonate was used as the CO₂ source. For each amino acid, the maximum carbamate yield, the apparent rate constant for the carbamate formation k_app, and the rate constants for the formation k₁ and the breakdown k_?1 of the carbamate were estimated. Plots of log k₁ or log k_?1 versus pK_a of amino acids indicated that the formation rate k₁ increased with the basicity (pK_a) of amino acid, while the decomposition rate k_?1 decreased. A Br?nsted β value of 0.39 was obtained from the former plot, being in good agreement with the previously reported ones (0.26–0.43). The observed negative pK_a dependence of log k_?1 (Br?nsted α = 0.34) is reasonable, because the carbamate decomposition is acid‐catalyzed and the steady‐state concentration of H⁺ should be higher for weaker basic amines. The charge (σ) and the lone‐pair energy (E_N) at the nitrogen atom of the amino group were calculated. Although log k₁ correlated with σ and E_N, log k_?1 was unrelated with both of these parameters. Considering that the carbamate formation (k₁) is not only base‐catalyzed but should also be promoted by the nucleophilicity of the amino nitrogen, its correlation with σ and E_N in addition to pK_a is rational. The irrelevance of log k_?1 to σ and E_N is not surprising, because σ and E_N are not a direct measure of [H⁺] of the solution. Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of the nuclear charge of a fast structural ion on its internal effective stopping in collisions with atoms

The energy losses of fast structural ions in collisions with atoms have been considered in the eikonal approximation. The structural ions are ions consisting of a nucleus and a certain number of electrons bound to it. The effect of nuclear charge Z of the ion on its effective deceleration κ^(p) (energy losses associated with excitation of only intrinsic ion shells) has been analyzed. It is shown that the allowance for the interaction of an atom with the ion nucleus for Z _a Z/v > 1, where Z _a is the charge of the atomic nucleus and v is the velocity of collisions in atomic units, considerably affects the value of κ^(p), which generally necessitates taking into account nonperturbatively the effect of both charges Z _a and Z on κ^(p).     

The role of substituents on the addition of muonium to aromatics: As seen through muonium-radicals in allyl benzene compared to styrene,and from hammett parameters in aqueous solution

Muonium-radicals resulting from insertion into the benzene ring are found to be much more prevalent in allyl benzene (C₆H₅CH₂CH=CH₂) than in styrene (C₆H₅CH=CH₂). The salient implication of this comparison is that intramolecular rearrangements preceeded the μSR observation for the case of styrene. In turn, this suggests that muonium-containing free radicals, as seen directly by kilogauss transverse field μSR, are not necessarily theprimary radicals. Therefore, the elucidation of mechanism (and identification of the precursor) of Mu-radical formation is further complicated by the fact that the observations may refer to thermodynamically more stable secondary radicals-those resulting from a variety of intra-or inter-molecular relaxations or exchanges. Primary kinetic selectivities of thermalized muonium atom addition reactions can be determined, however, through the substituent effect on the Hammett linear free energy parameter in dilute solution. Results have been obtained for substituted benzenes and benzoic acids. Muonium apparently has a mild nucleophilic character. And, most interestingly, this is opposite to that of its heavy isotope hydrogen.