We use a combination of x-ray diffraction, total scattering, and quantum mechanical calculations to determine the mechanism responsible for hydration-driven contraction in ZrW_{2}O_{8}. The inclusion of H_{2}O molecules within the ZrW_{2}O_{8} network drives the concerted formation of new WâO bonds to give one-dimensional (âWâOâ)_{n} strings. The topology of the ZrW_{2}O_{8} network is such that there is no unique choice for the string trajectories: the same local changes in coordination can propagate with a large number of different periodicities. Consequently, ZrW_{2}O_{8}·H_{2}O is heavily disordered, with each configuration of strings forming a dense aperiodic "spaghetti." This new connectivity contracts the unit cell via large shifts in the Zr and W atom positions. Fluctuations of the undistorted parent structure towards this spaghetti phase emerge as the key negative thermal expansion (NTE) phonon modes in ZrW_{2}O_{8} itself. The large relative density of NTE phonon modes in ZrW_{2}O_{8} actually reflects the degeneracy of volume-contracting spaghetti excitations, itself a function of the particular topology of this remarkable material.
Controlled assembly of two-dimensional (2D) supramolecular organic frameworks (SOFs) has been demonstrated through a binary strategy in which 1,4-bis-(4-(3,5-dicyano-2,6-dipyridyl)pyridyl)naphthalene (2), generated in situ by oxidative dehydrogenation of 1,4-bis-(4-(3,5-dicyano-2,6-dipyridyl)dihydropyridyl)naphthalene (1), is coupled in a 1:1 ratio with terphenyl-3,3',4,4'-tetracarboxylic acid (3; to form SOF-8), 5,5'-(anthracene-9,10-diyl)diisophthalic acid (4; to form SOF-9), or 5,5'-bis-(azanediyl)-oxalyl-diisophthalic acid (5; to form SOF-10). Complementary O-H···N hydrogen bonds assemble 2D 63-hcb (honeycomb) subunits that pack as layers in SOF-8 to give a three-dimensional (3D) supramolecular network with parallel channels hosting guest DMF (DMF = N,N'-dimethylformamide) molecules. SOF-9 and SOF-10 feature supramolecular networks of 2D â 3D inclined polycatenation of similar hcb layers as those in SOF-8. Although SOF-8 suffers framework collapse upon guest removal, the polycatenated frameworks of SOF-9 and SOF-10 exhibit excellent chemical and thermal stability, solvent/moisture durability, and permanent porosity. Moreover, their corresponding desolvated (activated) samples SOF-9a and SOF-10a display enhanced adsorption and selectivity for CO2 over N2 and CH4. The structures of these activated compounds are well described by quantum chemistry calculations, which have allowed us to determine their mechanical properties, as well as identify their soft deformation modes and a large number of low-energy vibration modes. These results not only demonstrate an effective synthetic platform for porous organic molecular materials stabilized solely by primary hydrogen bonds but also suggest a viable means to build robust SOF materials with enhanced gas uptake capacity and selectivity.
We study two Kitaev-Heisenberg t-J-like models on a honeycomb lattice, focusing on the zigzag magnetic phase of Na(2)IrO(3), and investigate hole motion by exact diagonalization and variational methods. The spectral functions are quite distinct from those of cuprates and are dominated by large incoherent spectral weight at high energy, almost independent of the microscopic parameters-a universal and generic feature for zigzag magnetic correlations. We explain why quasiparticles at low energy are strongly suppressed in the photoemission spectra and determine an analog of a pseudogap. We point out that the qualitative features of the predominantly incoherent spectra obtained within the two different models for the zigzag phase are similar, and they have a remarkable similarity to recently reported angular resolved photoemission spectra for Na(2)IrO(3).
Bosonic and fermionic Hubbard models on the checkerboard lattice are studied numerically for infinite on-site repulsion. At particle density n=1/4 and strong nearest-neighbor repulsion, insulating Valence-Bond crystals (VBC) of resonating particle pairs are stabilized. Their melting into superfluid or metallic phases under increasing hopping is investigated at T=0 K. We identify a novel and unconventional commensurate VBC supersolid region, precursor to the melting of the bosonic crystal. Hardcore bosons (spins) are compared to fermions (electrons), as well as positive to negative (frustrating) hoppings.
