Charge Transport in the Presence of Correlations and Disorder: Organic Conductors and Manganites.

One of the most fascinating aspects of condensed matter is its ability to conduct electricity, which is particularly pronounced in conventional metals such as copper or silver. Such behavior stems from a strong tendency of valence electrons to delocalize in a periodic potential created by ions in the crystal lattice of a given material. In many advanced materials, however, this basic delocalization process of the valence electrons competes with various processes that tend to localize these very same valence electrons, thus driving the insulating behavior. The two such most important processes are the Mott localization, driven by strong correlation effects among the valence electrons, and the Anderson localization, driven by the interaction of the valence electrons with a strong disorder potential. These two localization processes are almost exclusively considered separately from both an experimental and a theoretical standpoint. Here, we offer an overview of our long-standing research on selected organic conductors and manganites, that clearly show the presence of both these localization processes. We discuss these results within existing theories of Mott-Anderson localization and argue that such behavior could be a common feature of many advanced materials.

Magnesium ions reversibly bind to DNA double stranded helix in thin films.

Effects of magnesium (Mg2+) ions on the stability and structural properties of double-stranded DNA are vitally important for DNA folding and functional behavior. Complementing our previous study on highly hydrated thin films of DNA with sodium counterions, with no buffer (pH ≈ 6) and surrounded with Mg2+ cations, here we use Fourier transform infrared spectroscopy and band shape analysis to explore in detail the vibrational signatures of DNA-magnesium interaction in the case when DNA charges are neutralized solely by Mg2+ cations, hereafter called MgDNA. Ion atmosphere has been controlled by the magnesium to phosphate molar concentration ratio r which varied between 0.0067 and 10. For r = 0 we find that spectral features in the base region remain similar as in DNA, whereas changes in the backbone region indicate that the B conformation becomes fully stabilized. With increasing r a pronounced structural reshaping occurs in the phosphate backbone region indicating a blue shift of the asymmetric band, while the symmetric band does not show any displacement in frequency. The band shape analysis of overlapping peaks in the respective phosphate regions demonstrates that the number of constituent modes as well as their positions in frequency do not change, whereas their intensities and bandwidths display disparate changes. The results reflect a variety of local environments at the DNA backbone due to a heterogeneous ion atmosphere with randomly distributed magnesium ions and local patterns of hydrogen bonds which change with increasing r. Remarkably, after crowded r = 10 ion atmosphere is depleted, Mg induced spectral changes vanish and structural features of MgDNA (r ≈ 0) are fully restored. Overall results strongly suggest that in MgDNA on highly hydrated thin films the hydrogen-base pairing remains preserved and that Mg2+ ions, similar to sodium ions, retain their mobility and interact with double helix via water-mediated electrostatic forces.

New insights into the structural properties of κ-(BEDT-TTF)2Ag2(CN)3 spin liquid.

Here, the first accurate study is presented of the room-temperature and 100 K structures of one of the first organic spin liquids, κ-(BEDT-TTF)2Ag2(CN)3. It is shown that the monoclinic structure determined previously is only the average one. It is shown that the exact structure presents triclinic symmetry with two non-equivalent dimers in the unit cell. But surprisingly this does not lead to a sizeable charge disproportionation between dimers. The difference from the analogue compound κ-(BEDT-TTF)2Cu2(CN)3 which also presents a spin liquid phase is discussed in detail. The data provided here show the importance of the anionic layer and in particular the transition metal position in the process of symmetry breaking. The possible impact of the symmetry breaking, albeit weak, on the spin-liquid mechanism and the influence of various disorders on the physical properties of this system is also discussed.

Effect of magnesium ions on the structure of DNA thin films: an infrared spectroscopy study.

Utilizing Fourier transform infrared spectroscopy we have investigated the vibrational spectrum of thin dsDNA films in order to track the structural changes upon addition of magnesium ions. In the range of low magnesium concentration ([magnesium]/[phosphate] = [Mg]/[P] < 0.5), both the red shift and the intensity of asymmetric PO2 stretching band decrease, indicating an increase of magnesium-phosphate binding in the backbone region. Vibration characteristics of the A conformation of the dsDNA vanish, whereas those characterizing the B conformation become fully stabilized. In the crossover range with comparable Mg and intrinsic Na DNA ions ([Mg]/[P] ≈ 1) B conformation remains stable; vibrational spectra show moderate intensity changes and a prominent blue shift, indicating a reinforcement of the bonds and binding in both the phosphate and the base regions. The obtained results reflect the modified screening and local charge neutralization of the dsDNA backbone charge, thus consistently demonstrating that the added Mg ions interact with DNA via long-range electrostatic forces. At high Mg contents ([Mg]/[P] > 10), the vibrational spectra broaden and show a striking intensity rise, while the base stacking remains unaffected. We argue that at these extreme conditions, where a charge compensation by vicinal counterions reaches 92-94%, DNA may undergo a structural transition into a more compact form.