Halophilic reactions of a stable silylene with chloro and bromocarbons

A number of disilanes have been synthesized from a stable silylene, 1 (N,N'-di-tert-butyl-1,3-diaza-2-silacyclopent-4-en-2-ylidene), and a variety of halocarbons. It is proposed that disilane formation is a result of an initial halophilic interaction between the silylene and halocarbon. Formation of disilanes from 1 and CCl4, 2a, CHCl3, 2b, CH2Cl2, 2c, benzyl chloride, 2d, and bromobenzene, 5, are described here. An X-ray crystal structure of 2b was determined.     

Conformation-dependent state selectivity in O-O cleavage of ONOONO: an "inorganic cope rearrangement" helps explain the observed negative activation energy in the oxidation of nitric oxide by dioxygen

ONOONO has been proposed as an intermediate in the oxidation of nitric oxide by dioxygen to yield nitrogen dioxide. The O-O bond breaking reactions of this unusual peroxide, and subsequent rearrangements, were evaluated using CBS-QB3 and B3LYP/6-311G hybrid density functional theory. The three stable conformers (cis,cis-, cis,trans-, and trans,trans-ONOONO, based on the O-N-O-O dihedral angles of either approximately 0 degrees or approximately 180 degrees ) are predicted to have very different O-O cleavage barriers: 2.4, 13.0, and 29.8 kcal/mol, respectively. These large differences arise because bond breaking leads to correlation of the nascent NO(2) fragments with either the ground (2)A(1) state or the excited (2)B(2) state of NO(2), depending on the starting ONOONO conformation. A cis-oriented NO(2) fragment correlates with the (2)A(1) state, whereas a trans-oriented NO(2) fragment correlates with the (2)B(2) state. Each NO(2) fragment that correlates with (2)A(1) lowers the O-O homolysis energy by approximately 15 kcal/mol, similar to the approximately 17-25 kcal/mol (2)A(1) --> (2)B(2) energy difference in NO(2). Hence, this provides an unusual example of conformation-dependent electronic state selectivity. The O-O bond homolysis of cis,cis-ONOONO is particularly interesting because it has a very low barrier and arises from the most stable ONOONO conformer, and also due to obvious similarities to the well-known [3,3]-sigmatropic shift of 1,5-hexadiene, i.e., the Cope rearrangement. As an additional proof of our state selectivity postulate, a comparison is also made to breakage of the O-O bond of cis,cis-formyl peroxide, where no significant stabilization of the transition state is available because the (2)A(1) and (2)B(2) states of formyloxy radical are near-degenerate in energy. In the case of trans,trans-ONOONO, the O-O bond breaking transition state is a concerted rearrangement yielding O(2)NNO(2), whereas for cis,cis- and cis,trans-ONOONO, the initially formed NO(2) radical pairs can undergo further rearrangement to yield ONONO(2). It is proposed that previous spectroscopic observations of certain N=O stretching frequencies in argon-matrix-isolated products from the reaction of NO with O(2) (or (18)O(2)) are likely from ONONO(2), not the OONO radical as reported.     

Observation of unusual surface ordering in a uniaxial Sm-A phase formed by a highly biaxial compound

We have studied one banana-shaped compound using null-transmission ellipsometry. By studying free-standing films of various thicknesses we confirm that this compound exhibits the Sm-A phase. This is the first banana-shaped compound with a relatively small bend angle (approximately 140 degrees) in which a uniaxial phase has been observed. At the lower temperature end of the Sm-A phase we observe unusual ordering at the surface of the film.     

Balancing families of sets

Given k finite sets S₁,…,S_k, to what extent is it possible to partition their union into two parts A and B in such a way that, for each j, S_j ∩ A and S_j ∩ B contain approximately the same number of elements? Bounds are found for this and similar questions.     

Step structures on III-V phosphide (001) surfaces: how do steps and Sb affect CuPt ordering of GaInP2?

The observation of III-V phosphide (001)-(2 x 2) surfaces makes it possible to solve a long standing mystery of step structures. First-principles calculations show that a bulklike type-B step on a hydrogenated 2 x 2 surface is more stable than a rebonded one by 1.1 eV/unit step. In contrast, this energy difference for a H-free beta(2 x 4) surface is only 0.5 eV/unit step. The large difference explains why the CuPt ordering of GaInP is stronger in metal-organic chemical vapor deposition than in molecular beam epitaxy. However, a minute amount of Sb will preferentially attach to the 2 x 2 surface steps and induce additional step structures that cause ordering disruption.     

A nonmusical paradigm for identifying absolute pitch possessors

The ability to identify and reproduce sounds of specific frequencies is remarkable and uncommon. The etiology and defining characteristics of this skill, absolute pitch (AP), have been very controversial. One theory suggests that AP requires a specific type of early musical training and that the ability to encode and remember tones depends on these learned musical associations. An alternate theory argues that AP may be strongly dependent on hereditary factors and relatively independent of musical experience. To date, it has been difficult to test these hypotheses because all previous paradigms for identifying AP have required subjects to employ knowledge of musical nomenclature. As such, these tests are insensitive to the possibility of discovering AP in either nonmusicians or musicians of non-Western training. Based on previous literature in pitch memory, a paradigm is presented that is intended to distinguish between AP possessors and nonpossessors independent of the subjects' musical experience. The efficacy of this method is then tested with 20 classically defined AP possessors and 22 nonpossessors. Data from these groups strongly support the validity of the paradigm. The use of a nonmusical paradigm to identify AP may facilitate research into many aspects of this phenomenon.     

Intracochlear pressure measurements related to cochlear tuning

Pressure in turn one of the scala tympani (s.t.) was measured close to the basilar membrane (b.m.) and at additional positions as the pressure sensor approached and/or withdrew from the b.m. The s.t. pressure measured within about 100 microm of the b.m. varied rapidly in space at frequencies around the region's best frequency. Very close to the b.m. the s.t. pressure was tuned and scaled nonlinearly with sound level. The scala vestibuli (s.v.) pressure was measured at one position close to the stapes within seconds of the s.t. pressure and served primarily as a reference pressure. The driving pressure across the organ of Corti and the b.m. velocity were derived from the pressure data. Both were tuned and nonlinear. Therefore, their ratio, the specific acoustic impedance of the organ of Corti complex, was relatively untuned, and only subtly nonlinear. The impedance was inspected specifically for negative resistance (amplification) and resonance. Both were detected in some instances; taken as a whole, the current results constrain the possibilities for these qualities.     

Moving Wigner glasses and smectics: dynamics of disordered Wigner crystals

We examine the dynamics of driven classical Wigner solids interacting with quenched disorder from charged impurities. For strong disorder, the initial motion is plastic, in the form of crossing winding channels. For increasing drive, there is a reordering into a moving Wigner smectic with the electrons moving in separate 1D channels. These different dynamic phases can be related to the conduction noise and I(V) curves. For strong disorder, we show criticality in the voltage onset just above depinning. We obtain the dynamic phase diagram for driven Wigner solids and demonstrate a finite threshold of force for transverse sliding, recently observed experimentally.     

Structure of the liquid-crystal ferrielectric phases as determined by ellipsometry

The unit cell structures of two ferrielectric liquid-crystal phases are determined from ellipsometric studies of freestanding films in a nondistorting rotatable electric field. A highly biaxial mode with out-of-plane distortions describes all of the data from two different compounds. Qualitative and quantitative features of the data rule out alternate models. We also present a detailed explanation for apparent inconsistencies between previous resonant x-ray and optical experiments.