Photodissociation dynamics of the NO dimer. I. Theoretical overview of the ultraviolet singlet excited states

Molecular orbital theory and calculations are used to describe the ultraviolet singlet excited states of NO dimer. Qualitatively, we derive and catalog the dimer states by correlating them with monomer states, and provide illustrative complete active space self-consistent field calculations. Quantitatively, we provide computational estimates of vertical transition energies and absorption intensities with multireference configuration interaction and equations-of-motion coupled-cluster methods, and examine an important avoided crossing between a Rydberg and a valence state along the intermonomer and intramonomer stretching coordinates. The calculations are challenging, due to the high density of electronic states of various types (valence and Rydberg, excimer and charge transfer) in the 6-8 eV region, and the multiconfigurational nature of the ground state. We have identified a bright charge-transfer (charge-resonance) state as responsible for the broadband seen in UV absorption experiments. We also use our results to facilitate the interpretation of UV photodissociation experiments, including the time-resolved 6 eV photodissociation experiments to be presented in the next two papers of this series.     

Synthesis and characterization of imidocubanes with exocube Ge(IV) and Sn(IV) substituents: [M(mu3-NGeMe3)]4 (M = Sn, Ge, Pb); [Sn(mu3-NSnMe3)]4

The heteroleptic lithium amide, [(Me3Sn)(Me3Ge)NLi.(Et2O)]2 (2), reacts with MCl(2) (M = Sn, Ge, Pb) to yield the corresponding cubane complexes [M(mu3-NGeMe3)]4 [M = Sn (3), Ge (4), Pb (5)]. In an analogous reaction with SnCl2, the lithium stannylamide, [(Me3Sn)2NLi.(Et2O)]2 (1), produces the mixed-valent Sn congener [Sn(mu3-NSnMe3)]4 (6). All imidocubanes contain both di- and tetravalent group 14 metals that are bridged by N. These structures are comprised of M4N4 (M = Sn, Pb, Ge) cores that possess varying distortion from perfect cube geometry. The Pb derivative (5) exhibits enhanced volatility and vapor-phase integrity.     

Reactions of mixed silver-gold cluster cations AgmAun + (m+n=4,5,6) with CO: radiative association kinetics and density functional theory computations

Near thermal energy reactive collisions of small mixed metal cluster cations Ag(m)Au(n) (+) (m+n=4, 5, and 6) with carbon monoxide have been studied in the room temperature Penning trap of a Fourier transform ion-cyclotron-resonance mass spectrometer as a function of cluster size and composition. The tetrameric species AgAu(3) (+) and Ag(2)Au(2) (+) are found to react dissociatively by way of Au or Ag atom loss, respectively, to form the cluster carbonyl AgAu(2)CO(+). In contrast, measurements on a selection of pentamers and hexamers show that CO is added with absolute rate constants that decrease with increasing silver content. Experimentally determined absolute rate constants for CO adsorption were analyzed using the radiative association kinetics model to obtain cluster cation-CO binding energies ranging from 0.77 to 1.09 eV. High-level ab initio density functional theory (DFT) computations identifying the lowest-energy cluster isomers and the respective CO adsorption energies are in good agreement with the experimental findings clearly showing that CO binds in a "head-on" fashion to a gold atom in the mixed clusters. DFT exploration of reaction pathways in the case of Ag(2)Au(2) (+) suggests that exoergicities are high enough to access the minimum energy products for all reactive clusters probed.     

Radiation damage to alkyl chain monolayers on semiconductor substrates investigated by electron spectroscopy

Monolayers of alkyl chains, attached through direct Si-C bonds to Si(111), via phosphonates to GaAs(100) surfaces, or deposited as alkyl-silane monolayers on SiO2, are investigated by ultraviolet and inverse photoemission spectroscopy and X-ray absorption spectroscopy. Exposure to ultraviolet radiation from a He discharge lamp, or to a beam of energetic electrons, leads to significant damage, presumably associated with radiation- or electron-induced H-abstraction leading to carbon-carbon double-bond formation in the alkyl monolayer. The damage results in an overall distortion of the valence spectrum, in the appearance of (occupied) states above the highest occupied molecular orbital of the alkyl molecule, and in a characteristic (unoccupied state) pi resonance at the edge of the carbon absorption peak. These distortions present a serious challenge for the interpretation of the electronic structure of the monolayer system. We show that extrapolation to zero damage at short exposure times eliminates extrinsic features and allows a meaningful extraction of the density of state of the pristine monolayer from spectroscopy measurements.     

Saturated absorption spectroscopy of acetylene gas inside large-core photonic bandgap fiber

Saturated absorption spectroscopy is performed on the acetylene nu(1) + nu(3) band near 1532 nm inside photonic bandgap fibers of small (approximately 10 microm) and large (approximately 20 microm) core diameters. The observed linewidths are narrower in the 20 microm fiber and vary from 20 to 40 MHz depending on pressure and power. Variations in the background light transmission, attributed by others to surface modes, are significantly reduced in the 20 microm fiber. The optimum signal for use as a frequency reference in a 0.8 m long, 20 microm diameter fiber is found to occur at about 0.5 torr for 30 mW of pump power. The saturation power is found by modeling the propagation and attenuation of light inside the fiber.     

A rotation method which gives linear estimates for powers of the Ahlfors–Beurling operator

In [O. Dragičević, A. Volberg, Sharp estimate of the Ahlfors–Beurling operator via averaging martingale transforms, Michigan Math. J. 51 (2) (2003) 415–435] the Ahlfors–Beurling operator T was represented as an average of two-dimensional martingale transforms. The same result can be proven for powers Tⁿ. Motivated by [T. Iwaniec, G. Martin, Riesz transforms and related singular integrals, J. Reine Angew. Math. 473 (1996) 25–57], we deduce from here that Tⁿ_p are bounded from above by Cnp^*, . We further improve this estimate to obtain the optimal behaviour of the L^p norms in question.     

Towards biochips using microstructured optical fiber sensors

In this paper we present the first incorporation of a microstructured optical fiber (MOF) into biochip applications. A 16-mm-long piece of MOF is incorporated into an optic-fluidic coupler chip, which is fabricated in PMMA polymer using a CO₂ laser. The developed chip configuration allows the continuous control of liquid flow through the MOF and simultaneous optical characterization. While integrated in the chip, the MOF is functionalized towards the capture of a specific single-stranded DNA string by immobilizing a sensing layer on the microstructured internal surfaces of the fiber. The sensing layer contains the DNA string complementary to the target DNA sequence and thus operates through the highly selective DNA hybridization process. Optical detection of the captured DNA was carried out using the evanescent-wave-sensing principle. Owing to the small size of the chip, the presented technique allows for analysis of sample volumes down to 300 nL and the fabrication of miniaturized portable devices.      

An implicit box scheme for subsonic compressible flow with dissipative source term

We investigate the stability and convergence of an implicit box scheme for subsonic flows modelled by scalar conservation laws with dissipative and possibly stiff source terms. The scheme is proposed for solving transient gas flow problems in pipeline networks. Such networks are operated in the subsonic flow region and are characterized by pressure losses due to dissipative friction terms. We verify the properties stated by Kru?kov’s theorem (Kru?kov, Math. USSR-Sb. 10:217–243, 1970) for the approximate solution and prove its convergence to the entropy solution.     

Carnap,Goguen, and the Hyperontologies: Logical Pluralism and Heterogeneous Structuring in Ontology Design

This paper addresses questions of universality related to ontological engineering, namely aims at substantiating (negative) answers to the following three basic questions: (i) Is there a ‘universal ontology’?, (ii) Is there a ‘universal formal ontology language’?, and (iii) Is there a universally applicable ‘mode of reasoning’ for formal ontologies? To support our answers in a principled way, we present a general framework for the design of formal ontologies resting on two main principles: firstly, we endorse Rudolf Carnap’s principle of logical tolerance by giving central stage to the concept of logical heterogeneity, i.e. the use of a plurality of logical languages within one ontology design. Secondly, to structure and combine heterogeneous ontologies in a semantically well-founded way, we base our work on abstract model theory in the form of institutional semantics, as forcefully put forward by Joseph Goguen and Rod Burstall. In particular, we employ the structuring mechanisms of the heterogeneous algebraic specification language HetCasl for defining a general concept of heterogeneous, distributed, highly modular and structured ontologies, called hyperontologies. Moreover, we distinguish, on a structural and semantic level, several different kinds of combining and aligning heterogeneous ontologies, namely integration, connection, and refinement. We show how the notion of heterogeneous refinement can be used to provide both a general notion of sub-ontology as well as a notion of heterogeneous equivalence of ontologies, and finally sketch how different modes of reasoning over ontologies are related to these different structuring aspects.     

Iterated local search with Powell’s method: a memetic algorithm for continuous global optimization

In combinatorial solution spaces Iterated Local Search (ILS) turns out to be exceptionally successful. The question arises: is ILS also capable of improving the optimization process in continuous solution spaces? To demonstrate that hybridization leads to powerful techniques in continuous domains, we introduce a hybrid meta-heuristic that integrates Powell’s direct search method. It combines direct search with elements from population based evolutionary optimization. The approach is analyzed experimentally on a set of well known test problems and compared to a state-of-the-art technique, i.e., a restart variant of the Covariance Matrix Adaptation Evolution Strategy with increasing population sizes (G-CMA-ES). It turns out that the population-based Powell-ILS is competitive to the CMA-ES, in some cases even significantly faster and behaves more robust than the pure strategy of Powell in multimodal fitness landscapes. Further experiments on the perturbation mechanism, population sizes, and problems with noise complete the analysis of the hybrid methodology and lead to parameter recommendations.