Conformational studies of the triphenylphosphazenyl side chain in cyclophosphazenes. I. Crystal and molecular structure of N3P3C15(NPPh3)

The title compound, C t8H~sC15NaP4, crystallizes in the monoclinic space group P2~/n with a = 20.14 (2), b = 8.69 (1), c = 14.92 (2) A, fl = 98.8 (3) ° , Z = 4. The structure was determined from visual data and refined to R = 0-069 for 1450 reflections. The cyclophosphazene ring is non-planar. The exocyclic NPPh 3 group exhibits type I conformation [R. A. Shaw (1975). Pure Appl. Chem. 44, 317-341] in which the N-P bond is perpendicular to the adjacent P-CI bond.

Analysis of side-chain conformation in proteins

The crystal structures of a number of globular proteins are currently available. An analysis of the distribution of side-chains among different allowed conformations in these proteins has been carried out. The observed conformations of individual residues are discussed on the basis of well-known stereochemical criteria. The population distribution of side-chains in different allowed regions in conformational space can be explained largely on the basis of simple steric considerations. In addition to examining the conformational behaviour of individual residues, some population distributions of conformational angles of general interest involving groups of residues have also been analyzed.

Spin-1 Kitaev model in one dimension

We study a one-dimensional version of the Kitaev model on a ring of size N, in which there is a spin S > 1/2 on each site and the Hamiltonian is J Sigma(nSnSn+1y)-S-x. The cases where S is integer and half-odd integer are qualitatively different. We show that there is a Z(2)-valued conserved quantity W-n for each bond (n, n + 1) of the system. For integer S, the Hilbert space can be decomposed into 2N sectors, of unequal sizes. The number of states in most of the sectors grows as d(N), where d depends on the sector. The largest sector contains the ground state, and for this sector, for S=1, d=(root 5+1)/2. We carry out exact diagonalization for small systems. The extrapolation of our results to large N indicates that the energy gap remains finite in this limit. In the ground-state sector, the system can be mapped to a spin-1/2 model. We develop variational wave functions to study the lowest energy states in the ground state and other sectors. The first excited state of the system is the lowest energy state of a different sector and we estimate its excitation energy. We consider a more general Hamiltonian, adding a term lambda Sigma W-n(n), and show that this has gapless excitations in the range lambda(c)(1)<=lambda <=lambda(c)(2). We use the variational wave functions to study how the ground-state energy and the defect density vary near the two critical points lambda(c)(1) and lambda(c)(2).

Operationalizing Supply Chain vs. Supply Chain Competion

Competition is an immensely important area of study in economic theory, business and strategy. It is known to be vital in meeting consumers’ growing expectations, stimulating increase in the size of the market, pushing innovation, reducing cost and consequently generating better value for end users, among other things. Having said that, it is important to recognize that supply chains, as we know it, has changed the way companies deal with each other both in confrontational or conciliatory terms. As such, with the rise of global markets and outsourcing destinations, increased technological development in transportation, communication and telecommunications has meant that geographical barriers of distance with regards to competition are a thing of the past in an increasingly flat world. Even though the dominant articulation of competition within management and business literature rests mostly within economic competition theory, this thesis draws attention to the implicit shift in the recognition of other forms of competition in today’s business environment, especially those involving supply chain structures. Thus, there is popular agreement within a broad business arena that competition between companies is set to take place along their supply chains. Hence, management’s attention has been focused on how supply chains could become more aggressive making each firm in its supply chain more efficient. However, there is much disagreement on the mechanism through which such competition pitching supply chain against supply chain will take place. The purpose of this thesis therefore, is to develop and conceptualize the notion of supply chain vs. supply chain competition, within the discipline of supply chain management. The thesis proposes that competition between supply chains may be carried forward via the use of competition theories that emphasize interaction and dimensionality, hence, encountering friction from a number of sources in their search for critical resources and services. The thesis demonstrates how supply chain vs. supply chain competition may be carried out theoretically, using generated data for illustration, and practically using logistics centers as a way to provide a link between theory and corresponding practice of this evolving competition mode. The thesis concludes that supply chain vs. supply chain competition, no matter the conceptualization taken, is complex, novel and can be very easily distorted and abused. It therefore calls for the joint development of regulatory measures by practitioners and policymakers alike, to guide this developing mode of competition.

An infrared spectroscopic study of the low-spin-high-spin transition in FexMn1-x(Phen)2(NCS)2: A composition-induced change in the order of the spin-state transition

Infrared spectroscopy provides a valuable tool to investigate the spin-state transition in Fe(II) complexes of the type Fe(Phen)2(NCS)2. With progressive substitution of Fe by Mn, the first-order transition changes over to a second-order transition, with a high residual population of the high-spin state even at very low temperatures

Models of the proton spin structure

A phenomenological model of spin sharing by the constituents of a proton is constructed, based on the recent EMC measurement of the spin dependent structure function and knowledge of the unpolarized parton densities.

Hysteresis in model spin system

The aim of this paper is to construct a nonequilibrium statistical‐mechanics theory to study hysteresis in ferromagnetic systems. We study the hysteretic response of model spin systems to periodic magnetic fields H(t) as a function of the amplitude H0 and frequency Ω. At fixed H0, we find conventional, squarelike hysteresis loops at low Ω, and rounded, roughly elliptical loops at high Ω, in agreement with experiments. For the O(N→∞), d=3, (Φ2)2 model with Langevin dynamics, we find a novel scaling behavior for the area A of the hysteresis loop, of the form A∝H0.660Ω0.33. We carry out a Monte Carlo simulation of the hysteretic response of the two‐dimensional, nearest‐neighbor, ferromagnetic Ising model. These results agree qualitatively with the results obtained for the O(N) model.

Homonuclear NOE in spatially periodic spin systems

The nuclear Overhauser effect equations are solved analytically for a homonuclear group of spins whose sites are periodically arranged, including the special cases where the spins lie at the vertices of a regular polygon and on a one-dimensional lattice. t is shown that, for long correlation times, the equations governing magnetization transfer resemble a diffusion equation. Furthermore the deviation from exact diffusion is quantitatively related to the molecular tumbling correlation time. Equations are derived for the range of magnetization travel subsequent to the perturbation of a single spin in a lattice for both the case of strictly dipolar relaxation and the more general situation where additional T1 mechanisms may be active. The theory given places no restrictions on the delay (or mixing) times, and it includes all the spins in the system. Simulations are presented to confirm the theory.

Covalent attachment of two important dicopper(II) systems in a one-dimensional polymeric chain: An x-ray structure of [Cu2(en)2(OH)2·Cu2(O2CMe)4](PF6)2·0.5EtOH]α showing the shortest Cucdots, three dots, centeredCu Distance in the tetraacetato core

Reaction of Cu2(O2CMe)4(H2O)2 with 1,2-diaminoethane(en) in ethanol, followed by the addition of NH4PF6, led to the formation of a covalently linked 1D polymeric copper(II) title complex showing alternating [Cu2(en)2(OH)22+] and [Cu2(O2CMe)4] units in the chain and the shortest Cucdots, three dots, centeredCu separation of 2.558(2) Å in the tetraacetato core.

Excitation and relaxation energies of trans-stilbene: Confined singlet, triplet, and charged bipolarons

The π-electronic excitations and excited-state geometries of trans-stilbene (tS) are found by combining exact solutions of the Pariser-Parr-Pople (PPP) model and semiempirical Parametric Method 3 (PM3) calculations. Comprehensive comparisons with tS spectra are obtained and related to the fluorescence and topological alternation of poly(paraphenylenevinylene) (PPV). The one-photon absorption and triplet of tS correspond, respectively, to singlet and triplet bipolarons confined to two phenyls, while the tS2- ground state is a confined charged bipolaron. Independent estimates of the relaxation energy between vertical and adiabatic excitation show the bipolaron binding energy to depend on both charge and spin, as expected for interacting π electrons in correlated or molecular states. Complete configuration interaction within the PPP model of tS accounts for the singlet-triplet gap, for the fine-structure constants and triplet-triplet spectra, for two-photon transitions and intensities, and for one-photon spectra and the radiative lifetime, although the relative position of nearly degenerate covalent and ionic singlets is not resolved. The planar PM3 geometry and low rotational barrier of tS agree with resolved rotational and vibrational spectra in molecular beams. PM3 excitation and relaxation energies for tS bipolarons are consistent with experiment and with PPP results. Instead of the exciton model, we interpret tS excitations in terms of states that are localized on each ring or extended over an alternating chain, as found exactly in Hückel theory, and find nearly degenerate transitions between extended and localized states in the singlet, triplet, and dianion manifolds. The large topological alternation of the extended system increases the ionicity and interchanges the order of the lowest one- and two-photon absorption of PPV relative to polyenes.

Top-spin analysis of new scalar and tensor interactions in e(+)e(-) collisions with beam polarization

We utilize top polarization in the process e(+)e(-) -> t (t) over bar at the International Linear Collider ( ILC) with transverse beam polarization to probe interactions of the scalar and tensor type beyond the standard model and to disentangle their individual contributions. Ninety percent confidence level limits on the interactions with realistic integrated luminosity are presented and are found to improve by an order of magnitude compared to the case when the spin of the top quark is not measured. Sensitivities of the order of a few times 10(-3) TeV-2 for real and imaginary parts of both scalar and tensor couplings at root s = 500 and 800 GeV with an integrated luminosity of 500 fb(-1) and completely polarized beams are shown to be possible. A powerful model-independent framework for inclusive measurements is employed to describe the spin-momentum correlations, and their C, P, and T properties are presented in a technical appendix.