Theoretical study of the reaction of acrylonitrile on Si(001)

Two recent experiments for adsorbed acrylonitrile on the Si(001) surface reported different adsorption structures at 110 and 300 K. We investigate the reaction of acrylonitrile on Si(001) by first-principles density-functional calculations. We find that the so-called [4+2] structure in which acrylonitrile resides between two dimer rows is not only thermodynamically favored over other structural models but also easily formed via a precursor where the N atom of acrylonitrile is attached to the down atom of the Si dimer. The additional initial-state theory calculation for the C 1s core levels of adsorbed acrylonitrile provides an interpretation for the observed low- and room-temperature adsorption configurations in terms of the precursor and [4+2] structures, respectively.     

Hydrogen atom tunneling in triplet o-methylbenzocycloalkanones: effects of structure on reaction geometry and excited state configuration

The rates of phosphorescence decay of 4,7-dimethylindanone (2), 6,9-dimethylbenzosuberone (3), and several related compounds have been analyzed between 4 and 100 K to determine the contributions of intramolecular hydrogen atom tunneling from the o-methyl group to the excited state carbonyl oxygen. Changes in the benzocycloalkanone ring size from five to seven not only affect the geometry at the reaction center, but they also affect the electronic configuration of the triplet excited state in a significant manner. While the triplet state of 5,8-dimethyltetralone (1) in nonpolar glasses can be clearly described as having a predominant n,pi configuration, compounds 2 and 3 have a significantly larger contribution of the less reactive pi,pi state. 4,7-Dimethylindanone (2) is stable under cryogenic conditions and in solution at ambient temperature. In contrast, triplet lifetimes and product analysis indicate that 6,9-dimethylbenzosuberone (3) reacts by quantum mechanical tunneling at temperatures as low as 4 K. A surprisingly small isotope effect k(H)/k(D) approximately 1.1 between 4 and 50 K increases steadily up to k(H)/k(D) approximately 5.1 at 100 K. This unusual observation is interpreted in terms of a vibrationally activated quantum mechanical tunneling process with hydrogen atom transfer at the lowest temperatures being mediated by zero-point-energy reaction-promoting skeletal motions. Results presented here indicate that the combined effects of increasing pi,pi character and unfavorable reaction geometry contribute to the diminished reactivity of o-methyl ketones 2 and 3 as compared to those of tetralone 1.     

Dipole moments and near field potentials

Expressions are derived for the moments of electric and magnetic dipoles whose far field is equivalent to the Rayleigh term in the far field of a given radiating electromagnetic field. The equivalent dipole moments are expressed as integrals over an arbitrary closed surface of the near electromagnetic fields and simplification is achieved by rewriting these expressions in terms of the static potentials from which the near fields are derived. The results are valid regardless of the complexity of the field and the medium within the integration surface as long as the exterior is homogeneous, isotropic and source-free.Nomenclature B smooth closed bounded surface in 3-space - E, H radiating electric and magnetic field vectors - E ₀, H ₀ static near field limits of E and H - E ⁱ incident electric field vector - E ₀ ^t , H ₀ ^t total static field (incident plus scattered) - F, f arbitrary vector and scalar functions of position - k wave number - unit normal from B to exterior - p, m normalized electric and magnetic dipole moments - r position vector of field point with respect to origin in B - unit vector in direction of r - r magnitude of r - r _B position vector of point on B - V volume enclosed by B - , scalar potentials for E ₀ and H ₀ respectively - ^(e), ^(m) electric and magnetic Hertz vectors Research sponsored by the U.S. Air Force Office of Scientific Research under Grant No. AFOSR 69-1794.     

First principles calculation of anomalous Hall conductivity in ferromagnetic bcc Fe

We perform a first principles calculation of the anomalous Hall effect in ferromagnetic bcc Fe. Our theory identifies an intrinsic contribution to the anomalous Hall conductivity and relates it to the k-space Berry phase of occupied Bloch states. This dc conductivity has the same origin as the well-known magneto-optical effect, and our result accounts for experimental measurement on Fe crystals with no adjustable parameters.     

Instabilities in diamond under high shear stress

We investigate, through first-principles calculations, lattice instabilities induced in diamond by the application of high shear stresses. For shear stresses as low as 95 GPa a lattice instability will occur, leading to graphitelike layered structures. This effect is highly anisotropic. The reversal of the direction of the applied shear forces may cause a change of 80 GPa in the shear stress value at which the instability develops. The same reversal also causes different bonds to be broken, resulting in a drastic change in the orientation of the resulting graphitelike structures. We also find that an additional compressive stress of 50 GPa along the (111) direction does not eliminate the shear-induced instability.     

Structural reconfiguration and informal coordination in administrative organizations

This paper considers the problem of determining the optimal design of public organizations in terms of maximizing their reliability against institutional failures. To capture both the individual and the system-level aspects of organizational decisionmaking, first we present an analytical model that characterizes the optimal decision behavior of a single decision maker (unit, agent, in general: DM) in the context of a binary decision task. In this sense, reliability of a DM against the two possible error types: implementation of the wrong policy (error of comission, Type I error) and failure to act when it is necessary (error of omission, Type II error) are interpreted as the result of a particular decision strategy. Individual expertise is represented in the form of a Relative Operating Characteristic (ROC) curve that, in turn, depicts the necessary trade-off between the two errors when selecting an appropriate decision strategy. Component decisions are then combined along the lines of organizational structure which is described using a graph formalism. We show that the task of finding the best organizational design involves a joint optimization over structure and strategy, and implement the normative model in the context of a detailed example. Our numerical results suggest that when DMs coordinate their decision rules, there is little difference in the performance of various organizational structures.This work was supported by the Office of Naval Research under ONR contract #N0014-93-I-0793.