Z/E-photoisomerizations of olefins with 4npi- or (4n + 2)pi-electron substituents: zigzag variations in olefin properties along the T(1) state energy surfaces

[Figure: see text]. A quantum chemical study has been performed to assess changes in aromaticity along the T1 state Z/E-isomerization pathways of annulenyl-substituted olefins. It is argued that the point on the T1 energy surface with highest substituent aromaticity corresponds to the minimum. According to Baird (J. Am. Chem. Soc. 1972, 94, 4941), aromaticity and antiaromaticity are interchanged when going from S0 to T1. Thus, olefins with S0 aromatic substituents (set A olefins) will be partially antiaromatic in T1 and vice versa for olefins with S0 antiaromatic substituents (set B olefins). Twist of the C=C bond to a structure with a perpendicular orientation of the 2p(C) orbitals (3p*) in T1 should lead to regaining substituent aromaticity in set A and loss of aromaticity in set B olefins. This hypothesis is verified through quantum chemical calculations of T1 energies, geometries (bond lengths and harmonic oscillator measure of aromaticity), spin densities, and nucleus independent chemical shifts whose differences along the T1 PES display zigzag dependencies on the number of -electrons in the annulenyl substituent of the olefin. Aromaticity changes are reflected in the profiles of the T1 potential energy surfaces (T1 PESs) for Z/E-isomerizations because olefins in set A have minima at 3p* whereas those in set B have maxima at such structures. The proper combination (fusion) of the substituents of set A and B olefins could allow for design of novel optical switch compounds that isomerize adiabatically with high isomerization quantum yields.     

Where are the Sn atoms in LaSb2Snx, 0.1?x?∼0.75?

The composition range and (composite modulated) structure of compounds within the wide range non-stoichiometric LaSb₂Sn_x, 0.1?x?0.75, solid solution is carefully investigated via a combined electron diffraction, XRD and electron probe microanalysis study. Evidence for metastability of the LaSb₂Sn_x phase at the low x composition end of the solid solution is presented. Direct evidence is found for a reasonably (although by no means perfectly) well ordered Sn sub-structure which is, in general, mutually incommensurable with respect to a very well ordered underlying LaSb₂ sub-structure along both a and c directions. The overall (3+2)-d superspace group symmetry is given along with a discussion of the consequences as regards the arrangement of the Sn atoms. The Sn sub-structure c-axis cell dimension shows very little variation with composition x providing direct experimental evidence of the importance of Sn-Sn metallic bonding (along one-dimensional [001] Sn strings) for the stability of the phase.     

Spectral and scattering theory for a Schrödinger operator with a class of momentum-dependent long-range potentials

Let be the selfadjoint operator for the static electromagnetic field where W _j for 0, 1, 2, ..., n is a sum of (i) a short-range potential and (ii) a smooth long-range potential decreasing at as |x|^- with in (0, 1]. Then for >1/2, asymptotic completeness holds for the scattering system (H, H ₀).     

Studies in hydrogen bonding: simulation of the crystalline solids of ice, ammonia, and ammonia hydrate

The crystal structures of ice, ammonia and ammonia hydrate have been simulated with rigid molecules using the interatomic potential function EPEN/2 and the computer program WMIN. Structural parameters were adjusted to give structures with minimum energy. The hydrogen bonding in the simulated structures is compared with that in the experimental structures.     

q\bar q pair creation in a flux tube with confinement

We calculate the effect of radial confinement on the Schwinger pair production rate by solving the Dirac equation in a flux-tube cylinder containing a constant chromoelectric field in the longitudinal direction. We show how the Dirac equation separates into radial and longitudinal equations for a mass term which has an arbitrary radial dependence and introduce radial confinement by having a finite mass inside the cylinder and an infinitely large mass outside. The resulting boundary conditions are equivalent to the MIT boundary condition. The equations are solved analytically for a constant quark mass inside the flux-tube, which acts like a waveguide. The discretization of the transverse wave vector which has a continuous spectrum in the non-confined case leads to a large suppression of the Schwinger pair-production rate for small radii. The minimal radius where pairs are created decreases with increasing field strength. The suppression turns out to be larger for heavier quarks than for light quarks.     

Measurement of d sigma/dM and forward-backward charge asymmetry for high-mass Drell-Yan e(+)e(-) pairs from pp macro collisions at square root of s = 1.8 TeV

We report on a measurement of the mass dependence of the forward-backward charge asymmetry, A(FB), and production cross section d sigma/dM for e(+)e(-) pairs with mass M(ee)>40 GeV/c(2). The data sample consists of 108 pb(-1) of pp macro collisions at square root of s = 1.8 TeV taken by the Collider Detector at Fermilab during 1992-1995. The measured asymmetry and d sigma/dM are compared with the predictions of the standard model and a model with an extra Z' gauge boson.     

Tunable coupling of superconducting qubits

We study an LC circuit implemented using a current-biased Josephson junction (CBJJ) as a tunable coupler for superconducting qubits. By modulating the bias current, the junction can be tuned in and out of resonance and entangled with the qubits coupled to it. One can thus implement two-qubit operations by mediating entanglement. We consider the examples of CBJJ and charge-phase qubits. A simple recoupling scheme leads to a generalization to arbitrary qubit designs.     

New light on Hensel''s lemma

The historical development of Hensel's lemma is briefly discussed (Section 1). Using Newton polygons, a simple proof of a general Hensel's lemma for separable polynomials over Henselian fields is given (Section 3). For polynomials over algebraically closed, valued fields, best possible results on continuity of roots (Section 4) and continuity of factors (Section 6) are demonstrated. Using this and a general Krasner's lemma (Section 7), we give a short proof of a general Hensel's lemma and show that it is, in a certain sense, best possible (Section 8). All valuations here are non-Archimedean and of arbitrary rank. The article is practically self-contained.