The electronic structure of pyrazine. Configuration interaction calculations using an extended basis

Extensive ab initio double zeta basis set configuration interaction calculations have been carried out on the nπ^∗ and ππ^∗ states of pyrazine as well as on the low‐lying n and π cations. The calculations corroborate the validity of the valence bond (VB) model for the interaction of lone pair excitations proposed earlier by Wadt and Goddard. Good agreement (errors of ∼0.2 eV) with experiment is obtained (except for the higher‐lying 1ππ∗ states that possess significant ionic character). The calculations indicate that the order of increasing ionization potentials is ^2A_g(n), 2B_(1g)(π), 2B_(1u)(n), and ^2B_(2g)(π). The forbidden 1 ^1B_(2g)(nπ^∗) state is predicted to be 1.30 eV above the allowed 1^ 1B_(3u)(nπ^∗) state. Finally, the calculations indicate that the adiabatic excitation energies to the 1^ 3B_1(nπ^∗) and 1^ 3A_1(ππ^∗) states in pyridine should be nearly degenerate at ∼3.6 eV

A wide bandwidth free-electron laser with mode locking using current modulation

A new scheme for mode locking a free-electron laser (FEL) amplifier is proposed based on electron beam current modulation. It is found that certain properties of the original concept (Thompson and McNeil 2008 Phys. Rev. Lett. 100 203901), based on the energy modulation of electrons, are improved, including the spectral brightness of the source and the purity of the series of short pulses. Numerical comparisons are made between the new and old schemes and between a mode-locked FEL and a self-amplified spontaneous emission FEL. Illustrative examples using a hypothetical mode-locked FEL amplifier are provided. The ability to generate intense coherent radiation with a large bandwidth is demonstrated

Small-signal gain diagnostic measurements in a flowing CO2 pin discharge laser

Small-signal gain diagnostic measurements were conducted on closed loop, high power, carbon dioxide laser to assess the coupling between gas flow velocity and resonator saturation. Parameters investigated included optical cavity and discharge power. Results of gain measurements within and downstream of the excitation volume are presented for a laser gas composition He:N2:CO2 of 10:7:1 at 90 torr. The gain at constant discharge power was observed to be dependent upon discharge power level and time. An important result of this study is that the effects of gain swept downstream of the discharge region must be considered in the resonator design if efficient extraction of stored optical energy is desired

Transform-limited X-ray pulse generation from a high-brightness self-amplified spontaneous-emission free-electron laser

A method to achieve high-brightness self-amplified spontaneous emission (HB-SASE) in the free-electron laser (FEL) is described. The method uses repeated nonequal electron beam delays to delocalize the collective FEL interaction and break the radiation coherence length dependence on the FEL cooperation length. The method requires no external seeding or photon optics and so is applicable at any wavelength or repetition rate. It is demonstrated, using linear theory and numerical simulations, that the radiation coherence length can be increased by approximately 2 orders of magnitude over SASE with a corresponding increase in spectral brightness. Examples are shown of HB-SASE generating transform-limited FEL pulses in the soft x-ray and near transform-limited pulses in the hard x-ray. Such pulses may greatly benefit existing applications and may also open up new areas of scientific research

Comparison of the Projector Augmented-Wave, Pseudopotential, and Linearized Augmented-Plane-Wave Formalisms for Density-Functional Calculations of Solids

The projector augmented-wave (PAW) method was developed by Blöchl as a method to accurately and efficiently calculate the electronic structure of materials within the framework of density-functional theory. It contains the numerical advantages of pseudopotential calculations while retaining the physics of all-electron calculations, including the correct nodal behavior of the valence-electron wave functions and the ability to include upper core states in addition to valence states in the self-consistent iterations. It uses many of the same ideas developed by Vanderbilt in his soft pseudopotential\u27\u27 formalism and in earlier work by Blöchl in his generalized separable potentials,\u27\u27 and has been successfully demonstrated for several interesting materials. We have developed a version of the PAW formalism for general use in structural and dynamical studies of materials. In the present paper, we investigate the accuracy of this implementation in comparison with corresponding results obtained using pseudopotential and linearized augmented-plane-wave (LAPW) codes. We present results of calculations for the cohesive energy, equilibrium lattice constant, and bulk modulus for several representative covalent, ionic, and metallic materials including diamond, silicon, SiC, CaF2, fcc Ca, and bcc V. With the exception of CaF2, for which core-electron polarization effects are important, the structural properties of these materials are represented equally well by the PAW, LAPW, and pseudopotential formalisms

Mechanisms of two-color laser-induced field-free molecular orientation

Two mechanisms of two-color (\omega + 2\omega) laser-induced field-free molecular orientation, based on the hyperpolarizability and ionization depletion, are explored and compared. The CO molecule is used as a computational example. While the hyperpolarizability mechanism generates small amounts of orientation at intensities below the ionization threshold, ionization depletion quickly becomes the dominant mechanism as soon as ionizing intensities are reached. Only the ionization mechanism leads to substantial orientation (e.g. on the order of || > 0.1). For intensities typical of laser-induced molecular alignment and orientation experiments, the two mechanism lead to robust, characteristic timings of the field-free orientation wave-packet revivals relative to the the alignment revivals and the revival time. The revival timings can be used to detect the active orientation mechanism experimentally

Class-based probability estimation using a semantic hierarchy

This article concerns the estimation of a particular kind of probability, namely, the probability of a noun sense appearing as a particular argument of a predicate. In order to overcome the accompanying sparse-data problem, the proposal here is to define the probabilities in terms of senses from a semantic hierarchy and exploit the fact that the senses can be grouped into classes consisting of semantically similar senses. There is a particular focus on the problem of how to determine a suitable class for a given sense, or, alternatively, how to determine a suitable level of generalization in the hierarchy. A procedure is developed that uses a chi-square test to determine a suitable level of generalization. In order to test the performance of the estimation method, a pseudo-disambiguation task is used, together with two alternative estimation methods. Each method uses a different generalization procedure; the first alternative uses the minimum description length principle, and the second uses Resnik's measure of selectional preference. In addition, the performance of our method is investigated using both the standard Pearson chi-square statistic and the log-likelihood chi-square statistic

Space Station Freedom ground data system: Design and operations

Over the previous year the Space Station Freedom (SSF) Program (SSFP) ground data distribution system has become independent of a number of data systems that were to have been provided by other National Aeronautics and Space Administration (NASA) programs. Consequently, the SSFP has outlined the basic architecture of a new data system dedicated to supporting SSF requirements. This has been accomplished through a complete redesign of the ground network and a reallocation of selected functions. There are a number of aspects of the new ground data distribution system that are unique among NASA programs. These considerations make SSF ground data distribution one of the most extensive and complex data management challenges encountered in the arena of Space Operations. A description of this system comprises the main focus of the paper