Dynamics of ligand substitution in labile cobalt complexes resolved by ultrafast T-jump

Ligand exchange of hydrated metal complexes is common in chemical and biological systems. Using the ultrafast T-jump, we examined this process, specifically the transformation of aqua cobalt (II) complexes to their fully halogenated species. The results reveal a stepwise mechanism with time scales varying from hundreds of picoseconds to nanoseconds. The dynamics are significantly faster when the structure is retained but becomes rate-limited when the octahedral-to-tetrahedral structural change bottlenecks the transformation. Evidence is presented, from bimolecular kinetics and energetics (enthalpic and entropic), for a reaction in which the ligand assists the displacement of water molecules, with the retention of the entering ligand in the activated state. The reaction time scale deviates by one to two orders of magnitude from that of ionic diffusion, suggesting the involvement of a collisional barrier between the ion and the much larger complex

Gauge fields in (A)dS within the unfolded approach: algebraic aspects

It has recently been shown that generalized connections of the (A)dS space symmetry algebra provide an effective geometric and algebraic framework for all types of gauge fields in (A)dS, both for massless and partially-massless. The equations of motion are equipped with a nilpotent operator called $\sigma_-$ whose cohomology groups correspond to the dynamically relevant quantities like differential gauge parameters, dynamical fields, gauge invariant field equations, Bianchi identities etc. In the paper the $\sigma_-$-cohomology is computed for all gauge theories of this type and the field-theoretical interpretation is discussed. In the simplest cases the $\sigma_-$-cohomology is equivalent to the ordinary Lie algebra cohomology.Comment: 59 pages, replaced with revised verio

On electromagnetic interactions for massive mixed symmetry field

In this paper we investigate electromagnetic interactions for simplest massive mixed symmetry field. Using frame-like gauge invariant formulation we extend Fradkin-Vasiliev procedure, initially proposed for investigation of gravitational interactions for massless particles in AdS space, to the case of electromagnetic interactions for massive particles leaving in (A)dS space with arbitrary value of cosmological constant including flat Minkowski space. At first, as an illustration of general procedure, we re-derive our previous results on massive spin 2 electromagnetic interactions and then we apply this procedure to massive mixed symmetry field. These two cases are just the simplest representatives of two general class of fields, namely completely symmetric and mixed symmetry ones, and it is clear that the results obtained admit straightforward generalization to higher spins as well.Comment: 17 pages. Some clarifications added. Version to appear in JHE

The Coulomb phase shift revisited

We investigate the Coulomb phase shift, and derive and analyze new and more precise analytical formulae. We consider next to leading order terms to the Stirling approximation, and show that they are important at small values of the angular momentum $l$ and other regimes. We employ the uniform approximation. The use of our expressions in low energy scattering of charged particles is discussed and some comparisons are made with other approximation methods.Comment: 13 pages, 5 figures, 1 tabl

Heavy anion solvation of polarity fluctuations in Pnictides

Once again the condensed matter world has been surprised by the discovery of yet another class of high temperature superconductors. The discovery of iron-pnictide (FeAs) and chalcogenide (FeSe) based superconductors with a $T_c$ of up to 55 K is again evidence of how complex the many body problem really is, or in another view how resourceful nature is. The first reactions would of course be that these new materials must in some way be related to the copper-oxide based superconductors for which a large number of theories exist although a general consensus regarding the correct theory has not yet been reached. Here we point out that the basic physical paradigm of the new iron based superconductors is entirely different from the cuprates. Their fundamental properties, structural and electronic, are dominated by the exceptionally large pnictide polarizabilities

Light flavor baryon spectrum with higher order hyperfine interactions

We study the spectrum of light flavor baryons in a quark-model framework by taking into account the order $\mathrm{O}(\alpha_s^2)$ hyperfine interactions due to two-gluon exchange between quarks. The calculated spectrum agree better with the experimental data than the results from hyperfine interactions with only one-gluon exchange. It is also shown that two-gluon exchange hyperfine interactions bring a significantly improved correction to the Gell-Mann--Okubo mass formula. Two-gluon exchange corrections on baryon excitations (including negative parity baryons) are also briefly discussed.Comment: 31 latex pages, final version in journal publicatio