Bridge-localized HOMO-binding character of divinylanthracene-bridged dinuclear ruthenium carbonyl complexes: spectroscopic, spectroelectrochemical, and computational studies

The electronic properties of four divinylanthracene-bridged diruthenium carbonyl complexes [{RuCl(CO)(PMe3)3}2(μ[BOND]CH[DOUBLE BOND]CHArCH[DOUBLE BOND]CH)] (Ar=9,10-anthracene (1), 1,5-anthracene (2), 2,6-anthracene (3), 1,8-anthracene (4)) obtained by molecular spectroscopic methods (IR, UV/Vis/near-IR, and EPR spectroscopy) and DFT calculations are reported. IR spectroelectrochemical studies have revealed that these complexes are first oxidized at the noninnocent bridging ligand, which is in line with the very small ν(C[TRIPLE BOND]O) wavenumber shift that accompanies this process and also supported by DFT calculations. Because of poor conjugation in complex 1, except oxidized 1+, the electronic absorption spectra of complexes 2+, 3+, and 4+ all display the characteristic near-IR band envelopes that have been deconvoluted into three Gaussian sub-bands. Two of the sub-bands belong mainly to metal-to-ligand charge-transfer (MLCT) transitions according to results from time-dependent DFT calculations. EPR spectroscopy of chemically generated 1+–4+ proves largely ligand-centered spin density, again in accordance with IR spectra and DFT calculations results.

Centennial changes in solar activity and the response of galactic cosmic rays

There is a growing consensus that the eleven year modulation of galactic cosmic rays (GCRs) resulting from solar activity is related to interplanetary propagating diffusive barriers (PDBs). The source of these PDBs is not well understood and numerical models describing GCR modulation simulate their effect by scaling the diffusion tensor to the interplanetary magnetic field strength (IMF). The implications of a century-scale change in solar wind speed and open solar flux, for numerical modelling of GCR modulation and the reconstruction of GCR variations over the last hundred years are discussed. The dominant role of the solar non-axisymmetric magnetic field in both forcing longitudinal solar wind speed fluctuations at solar maximum and in increasing the IMF is discussed in the context of a long-term rise in the open solar magnetic flux.

Competition and dispersal in Pseudomonas aeruginosa

Dispersal plays a crucial role in a range of evolutionary and ecological processes; hence there is strong motivation to understand its evolution. One key prediction is that the relative benefits of dispersal should be greater when dispersing away from close relatives, because in this case dispersal has the additional benefit of alleviating competition with individuals who share the same dispersal alleles. We tested this prediction for the first time using experimental populations of the opportunistic pathogen Pseudomonas aeruginosa. We measured the fitness of isogenic genotypes that differed only in their dispersal behaviors in both clonal and mixed populations. Consistent with theory, the benefit of dispersal was much higher in clonal populations, and this benefit decreased with increasing growth rate costs associated with dispersal.

Heaps and Chains: Is the Chaining Argument for parity a sorites?

I argue that the Ruth Chang’s Chaining Argument for her parity view of value incomparability trades illicitly on the vagueness of the predicate ‘is comparable with’. Chang is alert to this danger and argues that the predicate is not vague, but this defense does not succeed. The Chaining Argument also faces a dilemma. The predicate is either vague or precise. If it is vague, then the argument is most plausibly a sorites. If it is precise, then the argument is either question begging or dialectically ineffective. I argue that no chaining-type argument can succeed.