Anomalous thermal expansion in 1D transition-metal cyanides: what makes the novel trimetallic cyanide Cu1/3Ag1/3Au1/3CN behave differently?

The structural dynamics of a quasi-one-dimensional (1D) mixed-metal cyanide, Cu1/3Ag1/3Au1/3CN, with intriguing thermal properties is explored. All the current known related compounds with straight-chain structures, such as group 11 cyanides CuCN, AgCN, AuCN and bimetallic cyanides MxM’1-xCN (M, M’ = Cu, Ag, Au), exhibit 1D negative thermal expansion (NTE) along the chains and positive thermal expansion (PTE) perpendicular to them. Cu1/3Ag1/3Au1/3CN exhibits similar PTE perpendicular to the chains, however PTE, rather than NTE, is also observed along the chains. In order to understand the origin of this unexpected behavior, inelastic neutron scattering (INS) measurements were carried out, underpinned by lattice-dynamical density-functional-theory (DFT) calculations. Synchrotron-based pair-distribution-function (PDF) analysis and 13C solid-state nuclear-magnetic-resonance (SSNMR) measurements were also performed to build an input structural model for the lattice dynamical study. The results indicate that transverse motions of the metal ions are responsible for the PTE perpendicular to the chains, as is the case for the related group 11 cyanides. However NTE along the chain due to the tension effect of these transverse motions is not observed. As there are different metal-to-cyanide bond lengths in Cu1/3Ag1/3Au1/3CN, the metals in neighboring chains cannot all be truly co-planar in a straight-chain model. For this system, DFT-based phonon calculations predict small PTE along the chain due to low-energy chain-slipping modes induced by a bond-rotation effect on the weak metallophilic bonds. However the observed PTE is greater than that predicted with the straight-chain model. Small bends in the chain to accommodate truly co-planar metals provide an alternative explanation for thermal behavior. These would mitigate the tension effect induced by the transverse motions of the metals and, as temperature increases and the chains move further apart, a straightening could occur resulting in the observed PTE. This hypothesis is further supported by unusual evolution in the phonon spectra, which suggest small changes in local symmetry with temperature

Chemistry and structure by design: ordered CuNi(CN)4 sheets with copper(II) in a square-planar environment

Layered copper–nickel cyanide, CuNi(CN)4, a 2-D negative thermal expansion material, is one of a series of copper(II)-containing cyanides derived from Ni(CN)2. In CuNi(CN)4, unlike in Ni(CN)2, the cyanide groups are ordered generating square-planar Ni(CN)4 and Cu(NC)4 units. The adoption of square-planar geometry by Cu(II) in an extended solid is very unusual

Magnetic Phase Transitions in the double spin-chains compound LiCu2O2\rm LiCu_2O_2

We report high-resolution x-ray diffraction, muon-spin-rotation spectroscopic and specific heat measurements in the double spin-chains compound $\rm LiCu_2O_2$. The x-ray diffraction results show that the crystal structure of $\rm LiCu_2O_2$ ~is orthorhombic down to T=10K. Anisotropic line-broadening of the diffraction peaks is observed, indicating disorder along the spin chains. Muon spin relaxation and specific heat measurements show that $\rm LiCu_2O_2$ \~undergoes a phase transition to a magnetic ordered state at $\rm T_1\sim24K$. The specific heat data exhibits a second $\rm \lambda$-like peak at $\rm T_2\sim22.5 K$, which increases with increasing magnetic field similarly way to that found in spin-ladder compounds.Comment: 6 pages, 6 fifures, to appear in Physica

Disorder induced phase segregation in La2/3Ca1/3MnO3 manganites

Neutron powder diffraction experiments on La2/3Ca1/3MnO3 over a broad temperature range above and below the metal-insulator transition have been analyzed beyond the Rietveld average approach by use of Reverse Monte Carlo modelling. This approach allows the calculation of atomic pair distribution functions and spin correlation functions constrained to describe the observed Bragg and diffuse nuclear and magnetic scattering. The results evidence phase separation within a paramagnetic matrix into ferro and antiferromagnetic domains correlated to anistropic lattice distortions in the vicinity of the metal-insulator transition.Comment: 3 pages, 4 figures. Submitted to Phys. Rev. Lett. Figure 1 replace

Extrinsic inhomogeneity effects in magnetic, transport and magnetoresistive properties of La_{1-x}Ca_{x}MnO_{3} (x\approx 0.33) crystal prepared by the floating zone method

The paper describes a study of the magnetic, transport and magnetoresistive properties of La_{1-x}Ca_{x}MnO_{3} (x\approx 0.33) crystals prepared by the floating-zone method. We found that these properties testify to rather good crystal perfection of the sample studied. In particular, a huge magnetoresistance ([R(0)-R(H)]/R(H) in the field H = 5 T is about 2680 %) is found near the Curie temperature (216 K). At the same time, some distinct features of measured properties indicate the influence of extrinsic inhomogeneities arising due to technological factors in the sample preparation. Analysis of the data obtained shows that these are rare grain boundaries and twins. Specific influence of the grain-boundary-like inhomogeneities on the transport and magnetoresistive properties are considered.Comment: Submitted to Physica

Structural response to O*-O' and magnetic transitions in orthorhombic perovskites

We present a temperature dependent single crystal x-ray diffraction study of twinned orthorhombic perovskites La1-xCaxMnO3, for x=0.16 and x=0.25. These data show the evolution of the crystal structure from the ferromagnetic insulating state to the ferromagnetic metallic state. The data are modelled in space group Pnma with twin relations based on a distribution of the b axis over three perpendicular cubic axes. The twin model allows full structure determination in the presence of up to six twin fractions using the single crystal x-ray diffraction data.Comment: 13 pages, including 13 figures and 2 table

Evidence for charge localization in the ferromagnetic phase of La_(1-x)Ca_(x)MnO_3 from High real-space-resolution x-ray diffraction

High real-space-resolution atomic pair distribution functions of La_(1-x)Ca_(x)MnO_3 (x=0.12, 0.25 and 0.33) have been measured using high-energy x-ray powder diffraction to study the size and shape of the MnO_6 octahedron as a function of temperature and doping. In the paramagnetic insulating phase we find evidence for three distinct bond-lengths (~ 1.88, 1.95 and 2.15A) which we ascribe to Mn^{4+}-O, Mn^{3+}-O short and Mn^{3+}-O long bonds respectively. In the ferromagnetic metallic (FM) phase, for x=0.33 and T=20K, we find a single Mn-O bond-length; however, as the metal-insulator transition is approached either by increasing T or decreasing x, intensity progressively appears around r=2.15 and in the region 1.8 - 1.9A suggesting the appearance of Mn^{3+}-O long bonds and short Mn^{4+}-O bonds. This is strong evidence that charge localized and delocalized phases coexist close to the metal-insulator transition in the FM phase.Comment: 8 pages, 8 postscript figures, submitted to Phys. Rev.