Elusiveness of bishomoaromaticity in anionic systems: the bicyclo[3.2.1]octa-3,6-dien-2-yl anion

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Colossal Effects in Transition Metal Oxides Caused by Intrinsic Inhomogeneities

The influence of quenched disorder on the competition between ordered states separated by a first-order transition is investigated. A phase diagram with features resembling quantum-critical behavior is observed, even using classical models. The low-temperature paramagnetic regime consists of coexisting ordered clusters, with randomly oriented order parameters. Extended to manganites, this state is argued to have a colossal magnetoresistance effect. A scale T* for cluster formation is discussed. This is the analog of the Griffiths temperature, but for the case of two competing orders, producing a strong susceptibility to external fields. Cuprates may have similar features, compatible with the large proximity effect of the very underdoped regime.Comment: 4 pages, 4 figure

Spin-phonon coupling in antiferromagnetic chromium spinels

The temperature dependence of eigenfrequencies and intensities of the IR active modes has been investigated for the antiferromagnetic chromium spinel compounds CdCr2O4, ZnCr2O4, ZnCr2S4, ZnCr2Se4, and HgCr2S4 by IR spectroscopy for temperatures from 5 K to 300 K. At the transition into the magnetically ordered phases, and driven by spin-phonon coupling, most compounds reveal significant splittings of the phonon modes. This is true for geometrically frustrated CdCr2O4, and ZnCr2O4, for bond frustrated ZnCr2S4 and for ZnCr2Se4, which also is bond frustrated, but dominated by ferromagnetic exchange. The pattern of splitting is different for the different compounds and crucially depends on the nature of frustration and of the resulting spin order. HgCr2S4, which is almost ferromagnetic, exhibits no splitting of the eigenfrequencies, but shows significant shifts due to ferromagnetic spin fluctuations.Comment: 15 pages, 6 figure

Stabilization of the alleged bishomoromatic bicyclo[3.2.1]octa-2,6-dienyl anion by counterion interactions and by hyperconjugation

Hyperconjugation and inductive effects, rather than homoaromaticity, are responsible for the stabilization of the title anion in the gas phase; interaction of the double bond with the Li+ gegenion in the endo geometry contributes additionally in solution

Phonon anomalies and charge dynamics in Fe_{1-x}Cu_{x}Cr_{2}S_{4} single crystals

A detailed investigation of phonon excitations and charge carrier dynamics in single crystals of Fe_{1-x}Cu_{x}Cr_{2}S_{4} (x = 0, 0.2, 0.4, 0.5) has been performed by using infrared spectroscopy. In FeCr_{2}S_{4} the phonon eigenmodes are strongly affected by the onset of magnetic order. Despite enhanced screening effects, a continuous evolution of the phonon excitations can be observed in the doped compounds with x = 0.2 (metallic) and x = 0.4, 0.5 (bad metals), but the effect of magnetic ordering on the phonons is strongly reduced compared to x = 0. The Drude-like charge-carrier contribution to the optical conductivity in the doped samples indicates that the colossal magneto-resistance effect results from the suppression of spin-disorder scattering.Comment: 8 pages, 6 figure

Optical phonons, spin correlations, and spin-phonon coupling in the frustrated pyrochlore magnets CdCr2O4 and ZnCr2O4

We report on infrared, Raman, magnetic susceptibility, and specific heat measurements on CdCr2O4 and ZnCr2O4 single crystals. We estimate the nearest-neighbor and next-nearest neighbor exchange constants from the magnetic susceptibility and extract the spin-spin correlation functions obtained from the magnetic susceptibility and the magnetic contribution to the specific heat. By comparing with the frequency shift of the infrared optical phonons above TN , we derive estimates for the spin-phonon coupling constants in these systems. The observation of phonon modes which are both Raman and infrared active suggest the loss of inversion symmetry below the Neel temperature in CdCr2O4 in agreement with theoretical predictions by Chern and coworkers [Phys. Rev. B 74, 060405 (2006)]. In ZnCr2O4 several new modes appear below TN, but no phonon modes could be detected which are both Raman and infrared active indicating the conservation of inversion symmetry in the low temperature phase.Comment: 11 pages, 13 figure