Large quantum fluctuations in the strongly coupled spin-1/2 chains of green dioptase: a hidden message from birds and trees

The green mineral dioptase Cu6Si6O18(H2O)6 has been known since centuries and plays an important role in esoteric doctrines. In particular, the green dioptase is supposed to grant the skill to speak with trees and to understand the language of birds. Armed with natural samples of dioptase, we were able to unravel the magnetic nature of the mineral (presumably with hidden support from birds and trees) and show that strong quantum fluctuations can be realized in an essentially framework-type spin lattice of coupled chains, thus neither frustration nor low-dimensionality are prerequisites. We present a microscopic magnetic model for the green dioptase. Based on full-potential DFT calculations, we find two relevant couplings in this system: an antiferromagnetic coupling J_c, forming spiral chains along the hexagonal c axis, and an inter-chain ferromagnetic coupling J_d within structural Cu2O6 dimers. To refine the J_c and J_d values and to confirm the proposed spin model, we perform quantum Monte-Carlo simulations for the dioptase spin lattice. The derived magnetic susceptibility, the magnetic ground state, and the sublattice magnetization are in remarkably good agreement with the experimental data. The refined model parameters are J_c = 78 K and J_d = -37 K with J_d/J_c ~ -0.5. Despite the apparent three-dimensional features of the spin lattice and the lack of frustration, strong quantum fluctuations in the system are evidenced by a broad maximum in the magnetic susceptibility, a reduced value of the Neel temperature T_N ~ 15 K >> J_c, and a low value of the sublattice magnetization m = 0.55 Bohr magneton. All these features should be ascribed to the low coordination number of 3 that outbalances the three-dimensional nature of the spin lattice.Comment: Dedicated to Stefan-Ludwig Drechsler on the occasion of his 60th birthday (9 pages, 6 figures

Anomalous dephasing of bosonic excitons interacting with phonons in the vicinity of the Bose-Einstein condensation

The dephasing and relaxation kinetics of bosonic excitons interacting with a thermal bath of acoustic phonons is studied after coherent pulse excitation. The kinetics of the induced excitonic polarization is calculated within Markovian equations both for subcritical and supercritical excitation with respect to a Bose-Einstein condensation (BEC). For excited densities n below the critical density n_c, an exponential polarization decay is obtained, which is characterized by a dephasing rate G=1/T_2. This dephasing rate due to phonon scattering shows a pronounced exciton-density dependence in the vicinity of the phase transition. It is well described by the power law G (n-n_c)^2 that can be understood by linearization of the equations around the equilibrium solution. Above the critical density we get a non-exponential relaxation to the final condensate value p^0 with |p(t)|-|p^0| ~1/t that holds for all densities. Furthermore we include the full self-consistent Hartree-Fock-Bogoliubov (HFB) terms due to the exciton-exciton interaction and the kinetics of the anomalous functions F_k= . The collision terms are analyzed and an approximation is used which is consistent with the existence of BEC. The inclusion of the coherent x-x interaction does not change the dephasing laws. The anomalous function F_k exhibits a clear threshold behaviour at the critical density.Comment: European Physical Journal B (in print

Magnetism of CuX2 frustrated chains (X = F, Cl, Br): the role of covalency

Periodic and cluster density-functional theory (DFT) calculations, including DFT+U and hybrid functionals, are applied to study magnetostructural correlations in spin-1/2 frustrated chain compounds CuX2: CuCl2, CuBr2, and a fictitious chain structure of CuF2. The nearest-neighbor and second-neighbor exchange integrals, J1 and J2, are evaluated as a function of the Cu-X-Cu bridging angle, theta, in the physically relevant range 80-110deg. In the ionic CuF2, J1 is ferromagnetic for theta smaller 100deg. For larger angles, the antiferromagnetic superexchange contribution becomes dominant, in accord with the Goodenough-Kanamori-Anderson rules. However, both CuCl2 and CuBr2 feature ferromagnetic J1 in the whole angular range studied. This surprising behavior is ascribed to the increased covalency in the Cl and Br compounds, which amplifies the contribution from Hund's exchange on the ligand atoms and renders J1 ferromagnetic. At the same time, the larger spatial extent of X orbitals enhances the antiferromagnetic J2, which is realized via the long-range Cu-X-X-Cu paths. Both, periodic and cluster approaches supply a consistent description of the magnetic behavior which is in good agreement with the experimental data for CuCl2 and CuBr2. Thus, owing to their simplicity, cluster calculations have excellent potential to study magnetic correlations in more involved spin lattices and facilitate application of quantum-chemical methods

Microscopic magnetic modeling for the SS=1/2 alternating chain compounds Na3_3Cu2_2SbO6_6 and Na2_2Cu2_2TeO6_6

The spin-1/2 alternating Heisenberg chain system Na$_3$Cu$_2$SbO$_6$ features two relevant exchange couplings: $J_{1a}$ within the structural Cu$_2$O$_6$ dimers and $J_{1b}$ between the dimers. Motivated by the controversially discussed nature of $J_{1a}$, we perform extensive density-functional-theory (DFT) calculations, including DFT+$U$ and hybrid functionals. Fits to the experimental magnetic susceptibility using high-temperature series expansions and quantum Monte Carlo simulations yield the optimal parameters $J_{1a}$ = $-$217 K and $J_{1b}$ = 174 K with the alternation ratio $\alpha = J_{1a}/J_{1b} \simeq$ $-$1.25. For the closely related system Na$_2$Cu$_2$TeO$_6$, DFT yields substantially enhanced $J_{1b}$, but weaker $J_{1a}$. The comparative analysis renders the buckling of the chains as the key parameter altering the magnetic coupling regime. Numerical simulation of the dispersion relations of the alternating chain model clarify why both antiferromagnetic and ferrromagnetic $J_{1a}$ can reproduce the experimental magnetic susceptibility data.Comment: published version: 11 pages, 8 figures, 5 tables + Supplemental materia

Crystal water induced switching of magnetically active orbitals in CuCl2

The dehydration of CuCl2*2(H2O) to CuCl2 leads to a dramatic change in magnetic behavior and ground state. Combining density functional electronic structure and model calculations with thermodynamical measurements we reveal the microscopic origin of this unexpected incident -- a crystal water driven switching of the magnetically active orbitals. This switching results in a fundamental change of the coupling regime from a three-dimensional antiferromagnet to a quasi one-dimensional behavior. CuCl2 can be well described as a frustrated J1-J2 Heisenberg chain with ferromagnetic exchange J1 and J2/J1 ~ -1.5 for which a helical ground state is predicted.Comment: 6 pages, 5 figures, 1 table (PRB, accepted

Chloroplast DNA analysis in oak stands (Quercus robur L.) in North Rhine-Westphalia with presumably Slavonian origin: Is there an association between geographic origin and bud phenology?

Slavonian oaks (Quercus robur subsp. slavonica) have been introduced into Germany in the second half of the 19th century from the lowlands of the rivers Save and Drava in today’s Croatia. If compared to indigenous oak stands, they are characterized by good growth, comparatively low seed production and a late bud burst. Based on the information of European-wide variation patterns at chloroplast DNA markers in oaks we adapted chloroplast microsatellites for the analysis of all oak stands of presumably Slavonian origin in the Münsterland and lower Rhine regions. We were able to distinguish between Slavonian haplotypes with no natural occurrence in the study area and indigenous types that do not occur in the Balkan region. A generally high differentiation among stands was observed at chloroplast markers (GST = 0.674). Based on the haplotype information and historic records we found that stands with Slavonian material have been established between the years 1878 and 1903. In a total of 910 analysed trees the Slavonian haplotypes 5, 2 or 17 were the most frequent ones but a considerable amount of samples with indigenous haplotype 1 or haplotype10 with presumed origin in Southwestern Europe was also present. A clear association between haplotype 2 and late bud burst was detected in adult stands and in a field trial established with seeds from Slavonian and indigenous oak stands. The information about the haplotype composition in all Slavonian stands can be used as reference for the certification of reproductive material. The analysis of cpDNA haploytpes in old oak stands that had been established before the introduction of foreign seed material can give valuable information for the identification of indigenous oak stands

Tracking chromosomal positions of oligomers - a case study with Illumina's BovineSNP50 beadchip

<p>Abstract</p> <p>Background</p> <p>High density genotyping arrays have become established as a valuable research tool in human genetics. Currently, more than 300 genome wide association studies were published for human reporting about 1,000 SNPs that are associated with a phenotype. Also in animal sciences high density genotyping arrays are harnessed to analyse genetic variation. To exploit the full potential of this technology single nucleotide polymorphisms (SNPs) on the chips should be well characterized and their chromosomal position should be precisely known. This, however, is a challenge if the genome sequence is still subject to changes.</p> <p>Results</p> <p>We have developed a mapping strategy and a suite of software scripts to update the chromosomal positions of oligomer sequences used for SNP genotyping on high density arrays. We describe the mapping procedure in detail so that scientists with moderate bioinformatics skills can reproduce it. We furthermore present a case study in which we re-mapped 54,001 oligomer sequences from Ilumina's BovineSNP50 beadchip to the bovine genome sequence. We found in 992 cases substantial discrepancies between the manufacturer's annotations and our results. The software scripts in the <monospace>Perl</monospace> and <monospace>R</monospace> programming languages are provided as supplements.</p> <p>Conclusions</p> <p>The positions of oligomer sequences in the genome are volatile even within one build of the genome. To facilitate the analysis of data from a GWAS or from an expression study, especially with species whose genome assembly is still unstable, it is recommended to update the oligomer positions before data analysis.</p

The Ca II infrared triplet's performance as an activity indicator compared to Ca II H and K

Aims. A large number of Calcium Infrared Triplet (IRT) spectra are expected from the GAIA- and CARMENES missions. Conversion of these spectra into known activity indicators will allow analysis of their temporal evolution to a better degree. We set out to find such a conversion formula and to determine its robustness. Methods. We have compared 2274 Ca II IRT spectra of active main-sequence F to K stars taken by the TIGRE telescope with those of inactive stars of the same spectral type. After normalizing and applying rotational broadening, we subtracted the comparison spectra to find the chromospheric excess flux caused by activity. We obtained the total excess flux, and compared it to established activity indices derived from the Ca II H & K lines, the spectra of which were obtained simultaneously to the infrared spectra. Results. The excess flux in the Ca II IRT is found to correlate well with $R_\mathrm{HK}'$ and $R_\mathrm{HK}^{+}$, as well as $S_\mathrm{MWO}$, if the $B-V$-dependency is taken into account. We find an empirical conversion formula to calculate the corresponding value of one activity indicator from the measurement of another, by comparing groups of datapoints of stars with similar B-V.Comment: 16 pages, 15 figures. Accepted for publication in Astronomy & Astrophysic