The Nature of the Chemical Bond. VII. The Calculation of Resonance Energy in Conjugated Systems

The quantum‐mechanical treatment previously applied to benzene, naphthalene, and the hydrocarbon free radicals is used in the calculation of extra resonance energy of conjugation in systems of double bonds, the dihydronaphthalenes and dihydroanthracenes, phenylethylene, stilbene, isostilbene, triphenylethylene, tetraphenylethylene, biphenyl, o, m, and p‐diphenylbenzene, and 1,3,5‐triphenylbenzene. The calculated values, which are in approximate agreement with empirical values from thermochemical data, are used in the discussion of chemical properties and in the formulation of rules regarding conjugation in overlapping systems

Ab-initio calculation of the effect of stress on the chemical activity of graphene

Graphene layers are stable, hard, and relatively inert. We study how tensile stress affects $\sigma$ and $\pi$ bonds and the resulting change in the chemical activity. Stress affects more strongly $\pi$ bonds that can become chemically active and bind to adsorbed species more strongly. Upon stretch, single C bonds are activated in a geometry mixing $120^{o}$ and $90^{o}$; an intermediate state between $sp^{2}$ and $sp^{3}$ bonding. We use ab-initio density functional theory to study the adsorption of hydrogen on large clusters and 2D periodic models for graphene. The influence of the exchange-correlation functional on the adsorption energy is discussed

X-ray photoelectron spectroscopy studies of non-stoichiometric superconducting NbB2+x

Polycrystalline samples of NbB2+x with nominal composition (B/Nb) = 2.0, 2.1, 2.2, 2.3, 2.4 and 2.5 were studied by X-ray photoelectron spectroscopy (XPS). The spectra revealed Nb and B oxides on the surface of the samples, mainly B2O3 and Nb2O5. After Ar ion etching the intensity of Nb and B oxides decreased. The Nb 3d5/2 and B 1s core levels associated with the chemical states (B/Nb) were identified and they do not change with etching time. The Binding Energy of the Nb 3d5/2 and B 1s core levels increase as boron content increases, suggesting a positive chemical shift in the core levels. On the other hand, analysis of Valence Band spectra showed that the contribution of the Nb 4d states slightly decreased while the contribution of the B 2p(pi) states increased as the boron content increased. As a consequence, the electronic and superconducting properties were substantially modified, in good agreement with band-structure calculations.Comment: 10 pages, 7 figures, 1 tabl

Structure and optical properties of high light output halide scintillators

Structural and optical properties of several high light output halide scintillators and closely related materials are presented based on first principles calculations. The optical properties are based on the Engel-Vosko generalized gradient approximation and the recently developed density functional of Tran and Blaha. The materials investigated are BaBr$_2$, BaIBr, BaCl$_2$, BaF$_2$, BaI$_2$, BiI$_3$, CaI$_2$, Cs$_2LiYCl$_6$, CsBa$_2$Br$_5$, CsBa$_2$I$_5$, K$_2$LaBr$_5$, K$_2$LaCl$_5$,K$_2$LaI$_5$, LaBr$_3$, LaCl$_3$, SrBr$_2$, and YI$_3$. For comparison results are presented for the oxide CdWO$_4$. We find that the Tran Blaha functional gives greatly improved band gaps and optical properties in this class of materials. Furthermore, we find that unlike CdWO$_4$, most of these halides are highly isotropic from an optical point of view even though in many cases the crystal structures and other properties are not. This general result is rationalized in terms of halide chemistry. Implications for the development of ceramic halide scintillators are discussed

Compressibilities, Force Constants, and Interatomic Distances of the Elements in the Solid State

Available data for the compressibilities of crystalline elements are used to calculate the force constants for the assumed Hooke's law interactions between adjacent atoms. On comparison of these constants and the equilibrium interatomic distances it is found that for many substances there holds the relation discovered by Badger for diatomic gas molecules: a linear relation between the reciprocal of the cube root of the force constant and the interatomic distance, for elements of a given row in the periodic table. Deviations from this relation are in the direction of increased compressibility. They are explained as resulting from changes in bond type (that is, in electronic structure) that permit the crystal to adjust itself to the increased pressure

Quantum fluctuations in the effective pseudospin-1/2 model for magnetic pyrochlore oxides

The effective quantum pseudospin-1/2 model for interacting rare-earth magnetic moments, which are locally described with atomic doublets, is studied theoretically for magnetic pyrochlore oxides. It is derived microscopically for localized Pr^{3+} 4f moments in Pr_2TM_2O_7 (TM = Zr, Sn, Hf, and Ir) by starting from the atomic non-Kramers magnetic doublets and performing the strong-coupling perturbation expansion of the virtual electron transfer between the Pr 4f and O 2p electrons. The most generic form of the nearest-neighbor anisotropic superexchange pseudospin-1/2 Hamiltonian is also constructed from the symmetry properties, which is applicable to Kramers ions Nd^{3+}, Sm^{3+}, and Yb^{3+} potentially showing large quantum effects. The effective model is then studied by means of a classical mean-field theory and the exact diagonalization on a single tetrahedron and on a 16-site cluster. These calculations reveal appreciable quantum fluctuations leading to quantum phase transitions to a quadrupolar state as a melting of spin ice for the Pr^{3+} case. The model also shows a formation of cooperative quadrupole moment and pseudospin chirality on tetrahedrons. A sign of a singlet quantum spin ice is also found in a finite region in the space of coupling constants. The relevance to the experiments is discussed.Comment: 18 pages including 14 figures; Comparison with the magnetization curve on Pr2Ir2O7 included; to appear in Phys. Rev.

Structural motifs of biomolecules

Biomolecular structures are assemblies of emergent anisotropic building modules such as uniaxial helices or biaxial strands. We provide an approach to understanding a marginally compact phase of matter that is occupied by proteins and DNA. This phase, which is in some respects analogous to the liquid crystal phase for chain molecules, stabilizes a range of shapes that can be obtained by sequence-independent interactions occurring intra- and intermolecularly between polymeric molecules. We present a singularityfree self-interaction for a tube in the continuum limit and show that this results in the tube being positioned in the marginally compact phase. Our work provides a unified framework for understanding the building blocks of biomolecules.Comment: 13 pages, 5 figure

Critical Temperature Tc and Charging Energy Ec between B-B layers of Superconducting diboride materials MgB2 in 3D JJA model

The diboride materials MB2 (M = Mg, Be, Pb, etc.) are discussed on the basis of the 3D Josephson junction array (JJA) model due to Kawabata-Shenoy-Bishop, in terms of the B-B layers in the diborides analogous to the Cu-O ones in the cuprates. We propose a possibility of superconducting materials with the MgB2-type structure which exhibit higher critical temperature Tc over 39K of MgB2. We point out a role of interstitial ionic atoms (e.g., Mg in MgB2) as capacitors between the B-B layers, which reduce the charging coupling energy in JJA.Comment: 3 pages, 1 figure included; to be published in J. Phys. Soc. Jpn. 70, No.10 (2001

Ground state of two unlike charged colloids: An analogy with ionic bonding

In this letter, we study the ground state of two spherical macroions of identical radius, but asymmetric bare charge ((Q_{A}>Q_{B})). Electroneutrality of the system is insured by the presence of the surrounding divalent counterions. Using Molecular Dynamics simulations within the framework of the primitive model, we show that the ground state of such a system consists of an overcharged and an undercharged colloid. For a given macroion separation the stability of these ionized-like states is a function of the difference ((\sqrt{N_{A}}-\sqrt{N_{B}})) of neutralizing counterions (N_{A}) and (N_{B}). Furthermore the degree of ionization, or equivalently, the degree of overcharging, is also governed by the distance separation of the macroions. The natural analogy with ionic bonding is briefly discussed.Comment: published versio

Realizing Colloidal Artificial Ice on Arrays of Optical Traps

We demonstrate how a colloidal version of artificial ice can be realized on optical trap lattices. Using numerical simulations, we show that this system obeys the ice rules and that for strong colloid-colloid interactions, an ordered ground state appears. We show that the ice rule ordering can occur for systems with as few as twenty-four traps and that the ordering transition can be observed at constant temperature by varying the barrier strength of the traps.Comment: 4 pages, 3 postscript figures; version to appear in Phys. Rev. Let