Slow crossover in YbXCu4 intermediate valence compounds

We compare the results of measurements of the magnetic susceptibility Chi(T), the linear coefficient of specific heat Gamma(T)=C(T)/T and 4f occupation number nf(T) for the intermediate valence compounds YbXCu4 (X = Ag, Cd, In, Mg, Tl, Zn) to the predictions of the Anderson impurity model, calculated in the non-crossing approximation (NCA). The crossover from the low temperature Fermi liquid state to the high temperature local moment state is substantially slower in the compounds than predicted by the NCA; this corresponds to the ''protracted screening'' recently predicted for the Anderson Lattice. We present results for the dynamic susceptibility, measured through neutron scattering experiments, to show that the deviations between theory and experiment are not due to crystal field effects, and we present x-ray-absorption fine-structure (XAFS) results that show the local crystal structure around the X atoms is well ordered, so that the deviations probably do not arise from Kondo Disorder. The deviations may correlate with the background conduction electron density, as predicted for protracted screening.Comment: Submitted to Physical Review B on June 7, 2000, accepted for publication November 2, 2000. Changes to the original manuscript include: 1) a discussion of the relation of the slow crossover to the conduction electron density; 2) a discussion of the relation of the reported results to earlier photoemission results; and, 3) minor editorial change

A new metalation complex for organic synthesis and polymerization reactions

Organometallic complex of N,N,N',N' tetramethyl ethylene diamine /TMEDA/ and lithium acts as metalation intermediate for controlled systhesis of aromatic organic compounds and polymer formation. Complex of TMEDA and lithium aids in preparation of various organic lithium compounds

Phase Separation in Lix_xFePO4_4 Induced by Correlation Effects

We report on a significant failure of LDA and GGA to reproduce the phase stability and thermodynamics of mixed-valence Li$_x$FePO$_4$ compounds. Experimentally, Li$_x$FePO$_4$ compositions ($0 \leq x \leq 1$) are known to be unstable and phase separate into Li FePO$_4$ and FePO$_4$. However, first-principles calculations with LDA/GGA yield energetically favorable intermediate compounds an d hence no phase separation. This qualitative failure of LDA/GGA seems to have its origin in the LDA/GGA self-interaction which de localizes charge over the mixed-valence Fe ions, and is corrected by explicitly considering correlation effects in this material. This is demonstrated with LDA+U calculations which correctly predict phase separation in Li$_x$FePO$_4$ for $U-J \gtrsim 3.5$eV. T he origin of the destabilization of intermediate compounds is identified as electron localization and charge ordering at different iron sites. Introduction of correlation also yields more accurate electrochemical reaction energies between FePO$_4$/Li$_x$FePO$_ 4$ and Li/Li$^+$ electrodes.Comment: 12 pages, 5 figures, Phys. Rev. B 201101R, 200

Control of nonenzymatic browning in intermediate-moisture foods

Series of compounds called humectants were found to decrease rate of browning when added to intermediate-moisture foods. Twenty percent level of humectant can increase shelf life of foods by factor of 5 or 6

Effects of magnetic doping and temperature dependence on phonon dynamics in CaFe\_{1-x}Co\_{x}AsF compounds (x = 0, 0.06, 0.12)

We report detailed measurements of composition as well as temperature dependence of the phonon density-of-states in a new series of FeAs compounds with composition CaFe1\_{1-x}Co\_{x}AsF (x = 0, 0.06, 0.12). The composition as well as temperature dependence of phonon spectra for CaFe\_{1-x}Co\_{x}AsF (x = 0, 0.06, 0.12) compounds have been measured using time of flight IN4C and IN6 spectrometers at ILL, France. The comparison of phonon spectra at 300 K in these compounds shows that acoustic phonon modes up to 12 meV harden in the doped compounds in comparison to the parent CaFeAsF. While intermediate energy phonon modes from 15 meV to 25 meV are also found to shift towards high energies only in the 12 % Co doped CaFeAsF compound. The experimental results for CaFe\_{1-x}Co\_{x}AsF (x = 0, 0.06, 0.12) are quite different from our previous phonon studies on parent and superconducting MFe2As2 (M=Ba, Ca, Sr) where low-energy acoustic phonon modes do not react with doping, while the phonon spectra in the intermediate range from 15 to 25 K are found to soften in these compounds. We argue that stronger spin phonon interaction play an important role for the emergence of superconductivity in these compounds. The lattice dynamics of CaFe\_{1-x}Co\_{x}AsF (x = 0, 0.06, 0.12) compounds is also investigated using the ab-initio as well as shell model phonon calculations. We show that the nature of the interaction between the Ca and the Fe-As layers in CaFeAsF compounds is quite different compared with our previous studies on CaFe2As2.Comment: 19 pages, 5 figure

Cycloadditions of cyclohexynes and cyclopentyne.

We report the strategic use of cyclohexyne and the more elusive intermediate, cyclopentyne, as a tool for the synthesis of new heterocyclic compounds. Experimental and computational studies of a 3-substituted cyclohexyne are also described. The observed regioselectivities are explained by the distortion/interaction model

Valence and magnetic ordering in intermediate valence compounds : TmSe versus SmB6

The intermediate valent systems TmSe and SmB6 have been investigated up to 16 and 18 GPa by ac microcalorimetry with a pressure (p) tuning realized in situ at low temperature. For TmSe, the transition from an antiferromagnetic insulator for p<3 GPa to an antiferromagnetic metal at higher pressure has been confirmed. A drastic change in the p variation of the Neel temperature (Tn) is observed at 3 GPa. In the metallic phase (p>3 GPa), Tn is found to increase linearly with p. A similar linear p increase of Tn is observed for the quasitrivalent compound TmS which is at ambiant pressure equivalent to TmSe at p=7 GPa. In the case of SmB6 long range magnetism has been detected above p=8 GPa, i.e. at a pressure slightly higher than the pressure of the insulator to metal transition. However a homogeneous magnetic phase occurs only above 10 GPa. The magnetic and electronic properties are related to the renormalization of the 4f wavefunction either to the divalent or the trivalent configurations. As observed in SmS, long range magnetism in SmB6 occurs already far below the pressure where a trivalent Sm3+ state will be reached. It seems possible, to describe roughly the physical properties of the intermediate valence equilibrium by assuming formulas for the Kondo lattice temperature depending on the valence configuration. Comparison is also made with the appearance of long range magnetism in cerium and ytterbium heavy fermion compounds.Comment: 22 pages including figure

Extended homologous series of Sn-O layered systems: a first-principles study

Apart from the most studied tin-oxide compounds, SnO and SnO2, intermediate states have been claimed to exist for more than a hundred years. In addition to the known homologous series (Seko et al., Phys. Rev. Lett. 100, 045702 (2008)), we here predict the existence of several new compounds with an O concentration between 50 % (SnO) and 67 % (SnO2). All these intermediate compounds are constructed from removing one or more (101) oxygen layers of SnO2. Since the van der Waals (vdW) interaction is known to be important for the Sn-Sn interlayer distances, we use a vdW-corrected functional, and compare these results with results obtained with PBE and hybrid functionals. We present the electronic properties of the intermediate structures and we observe a decrease of the band gap when (i) the O concentration increases and (ii) more SnO-like units are present for a given concentration. The contribution of the different atoms to the valence and conduction band is also investigated.Comment: 8 page

Pressure-tuning of the electron-phonon coupling: the insulator to metal transition in manganites

A comprehensive understanding of the physical origin of the unique magnetic and transport properties of A_(1-x)A'^xMnO_3 manganites (A = trivalent rare-earth and A' = divalent alkali-earth metal) is still far from being achieved. The complexity of these systems arises from the interplay among several competing interactions of comparable strength. Recently the electron-phonon coupling, triggered by a Jahn-Teller distortion of the MnO_6 octahedra, has been recognised to play an essential role in the insulator to metal transition and in the closely related colossal magneto-resistance. The pressure tuning of the octahedral distortion gives a unique possibility to separate the basic interactions and, at least in principle, to follow the progressive transformation of a manganite from an intermediate towards a weak electron-phonon coupling regime. Using a diamond anvil cell, temperature and pressure-dependent infrared absorption spectra of La_(0.75)Ca_(0.25)MnO_3 have been collected and, from the spectral weight analysis, the pressure dependence of the insulator to metal transition temperature T_IM has been determined for the first time up to 11.2 GPa. The T_IM(P) curve we proposed to model the present data revealed a universality character in accounting for the whole class of intermediate coupling compounds. This property can be exploited to distinguish the intermediate from the weak coupling compounds pointing out the fundamental differences between the two coupling regimes.Comment: 8 pages, 4 figure