Optical Spectroscopy of Orbital and Magnetic Excitations in Vanadates and Cuprates

Within the scope of this thesis the low-energy excitations of undoped Mott insulators RVO(3) with R = Y, Ho, and Ce, (Sr,Ca)CuO(2) and La(8)Cu(7)O(19) have been investigated by means of optical spectroscopy. The compounds RVO(3) with R = rare-earth ion recently have attracted a lot of interest because of their unusual structural, orbital, and magnetic properties. The compounds undergo a series of temperature-induced phase transitions accompanied by a change of orbital and magnetic order. Furthermore, it has been proposed that YVO(3) represents the first realization of a one-dimensional orbital liquid and an orbital Peierls phase, with a transition to an orbitally ordered phase at lower temperatures. In this thesis, we present the optical conductivity sig(w) of RVO(3) with R = Y, Ho, and Ce for energies from 0.1 to 1.6 eV as a function of temperature (10-300 K) and polarization of the incident light parallel to the crystallographic axes (sig_a, sig_b, sig_c). Our main experimental result is the observation of two absorption features at 0.55 eV in sig_a and 0.4 eV in sig_c which are assigned to collective orbital excitations, in contrast to conventional local crystal-field transitions. Altogether our results strongly suggest that in RVO(3) with R = Y, Ho, and Ce the orbital exchange interactions play a decisive role. In a second study we have investigated the magnetic excitations of low-dimensional quantum magnets, namely the spin chain (Sr,Ca)CuO(2) and the five-leg ladder La(8)Cu(7)O(19). For (Sr,Ca)CuO(2), two absorption features around 0.4 eV in sig_c (chain direction) and sig_b (inter-chain direction) are identified as magnetic contributions to the optical conductivity. The analysis of sig_c enables the very precise determination of the nearest-neighbor exchange coupling Jc as a function of temperature and Ca substitution. We have found Jc = (227 +- 4) meV for SrCuO(2) at low temperatures and no effect on Jc upon Ca-substitution of 10%. Furthermore, we ascertained that the theoretically predicted two-spinon-plus-phonon contribution describes roughly 74-97% of the observed spectral weight. We suggest that the remaining weight has to be ascribed to multi-spinon excitations. To explain the small magnetic absorption features in sig_b we sketch a new mechanism which gives rise to a dipole moment perpendicular to the chains when holes are virtually exchanged along the chain. In particular, we point out the possible relevance of this contribution to the optical conductivity of many quasi-1D quantum spin systems. Our data of La(8)Cu(7)O(19) are the first experimental result on the magnetic excitations of n-leg ladders (n > 2) at high energies. Amongst others, we compared our data with the well-investigated spectrum of the two-leg ladder and found a surprising resemblance. Although a detailed understanding of the observed line shape of the 5-leg ladder is missing up to now, our data strongly suggest the existence of bound states of magnetic excitations also in this system. The comparison of different low-dimensional S = 1/2 systems suggests that the magnetic excitations in the high-energy continua are similar and develop smoothly from 1D to 2D

Side Effects of Nitrification Inhibitors on Non Target Microbial Processes in Soils

Agricultural chemicals have been used extensively in modern agriculture and toxicological studies suggest a great potential for inducing undesirable effects on non target organisms. A model experiment was conducted in order to determine side effects of three nitrification inhibitors (NIs, 3,4dimethylpyrazolephosphate = DMPP, 4-Chlormethylpyrazole phosphate = ClMPP and dicyandiamide = DCD) on non target microbial processes in soils. Side effects and dose response curve of three NIs were quantified under laboratory conditions using silty clay, loam anda sandy soils. Dehydrogenase, dimethylsulfoxide reductase as well as nitrogenase activity (NA) and potential denitrification capacity were measured as common and specific non target microbial processes. The influence of 5-1000 times the base concentration, dose response curves were examined, and no observable effect level = NOEL, as well as effective dose ED10 and ED50 (10% and 50% inhibition) were calculated. The NOEL for microbial non target processes were about 30–70 times higher than base concentration in all investigated soils. The potential denitrification capacity revealed to be the most sensitive parameter. ClMPP exhibited the strongest influence on the non target microbial processes in the three soils. The NOEL, ED10 and ED50 values were higher in clay than in loamy or sandy soil. The NIs was the most effective in sandy soils.Keywords: microbial non target processes, nitrification inhibitors, soil enzyme

Toxicity of Nitrification Inhibitors on Dehydrogenase Activity in Soils

The objective of this research was to determine the effects of nitrification inhibitors (NIs) such as 3,4-dimethylpyrazolephosphate=DMPP, 4-Chlor-methylpyrazole phosphate=ClMPP and dicyandiamide,DCD) which might be expected to inhibit microbial activity, on dehydrogenase activity (DRA),in three different soils in laboratory conditions. Dehydrogenase activity were assessed via reduction of 2-p-Iodophenyl-3-p-nitrophenyl-5-phenyltetrazoliumchloride (INT). The toxicity and dose response curve of three NIs were quantified under laboratory conditions using a loamy clay, a sandy loam and a sandy soil. The quantitative determination of DHA was carried out spectrophotometrically. In all experiments, the influence of 5-1000 times the base concentration were examined. To evaluate the rate of inhibition with the increasing NI concentrations, dose reponse curves were presented and no observable effect level =NOEL, as well as effective dose ED10 and ED 50(10% and 50% inhibition) were calculated. The NOEL for common microbial activity such as DHA was about 30–70 times higher than base concentration in all investigated soils. ClMPP exhibited the strongest influence on the non target microbial processes in the three soils if it compare to DMPP and DCD. The NOEL,ED10 and ED50 values higher in clay than in loamy or sandy soil. The NIs were generally most effective in sandy soils. The three NIs considered at the present state of knowledge as environmentally safe in use

Dimensionality Control of Electronic Phase Transitions in Nickel-Oxide Superlattices

The competition between collective quantum phases in materials with strongly correlated electrons depends sensitively on the dimensionality of the electron system, which is difficult to control by standard solid-state chemistry. We have fabricated superlattices of the paramagnetic metal LaNiO3 and the wide-gap insulator LaAlO3 with atomically precise layer sequences. Using optical ellipsometry and low-energy muon spin rotation, superlattices with LaNiO3 as thin as two unit cells are shown to undergo a sequence of collective metalinsulator and antiferromagnetic transitions as a function of decreasing temperature, whereas samples with thicker LaNiO3 layers remain metallic and paramagnetic at all temperatures. Metal-oxide superlattices thus allow control of the dimensionality and collective phase behavior of correlated-electron systems

Digital modulation of the nickel valence state in a cuprate-nickelate heterostructure

Layer-by-layer oxide molecular beam epitaxy has been used to synthesize cuprate-nickelate multilayer structures of composition (La$_2$CuO$_4$)$_m$/LaO/(LaNiO$_3$)$_n$. In a combined experimental and theoretical study, we show that these structures allow a clean separation of dopant and doped layers. Specifically, the LaO layer separating cuprate and nickelate blocks provides an additional charge that, according to density functional theory calculations, is predominantly accommodated in the interfacial nickelate layers. This is reflected in an elongation of bond distances and changes in valence state, as observed by scanning transmission electron microscopy and x-ray absorption spectroscopy. Moreover, the predicted charge disproportionation in the nickelate interface layers leads to a thickness-dependent metal-to-insulator transition for $n=2$, as observed in electrical transport measurements. The results exemplify the perspectives of charge transfer in metal-oxide multilayers to induce doping without introducing chemical and structural disorder

Tunable Charge and Spin Order in PrNiO3_3 Thin Films and Superlattices

We have used polarized Raman scattering to probe lattice vibrations and charge ordering in 12 nm thick, epitaxially strained PrNiO$_3$ films, and in superlattices of PrNiO$_3$ with the band-insulator PrAlO$_3$. A carefully adjusted confocal geometry was used to eliminate the substrate contribution to the Raman spectra. In films and superlattices under tensile strain, which undergo a metal-insulator transition upon cooling, the Raman spectra reveal phonon modes characteristic of charge ordering. These anomalous phonons do not appear in compressively strained films, which remain metallic at all temperatures. For superlattices under compressive strain, the Raman spectra show no evidence of anomalous phonons indicative of charge ordering, while complementary resonant x-ray scattering experiments reveal antiferromagnetic order associated with a modest increase in resistivity upon cooling. This confirms theoretical predictions of a spin density wave phase driven by spatial confinement of the conduction electrons.Comment: PRL, in pres