Photolytic interference affecting two-photon laser-induced fluorescence detection of atomic oxygen in hydrocarbon flames

This study reports on photochemical interferences affecting atomic oxygen detection using two-photon laser-induced fluorescence at 226 nm. In contrast to previous studies in which molecular oxygen was proven to be the relevant photochemical precursor molecule in a hydrogen-fueled flame, the present investigations were carried out in a laminar diffusion flame of methane and air. The most significant interferences were found at the fuel side of the flame in the absence of molecular oxygen, and vibrationally excited carbon dioxide was identified as the most probable precursor molecule for the photochemical production of oxygen atoms. Received: 11 December 2002 / Revised version: 10 March 2003 / Published online: 16 April 2003 RID="*" ID="*"Corresponding author. Fax: +1-925/294-2595, E-mail: tbsette@sandia.gov     

The national ignition facility: path to ignition in the laboratory

The National Ignition Facility (NIF) is a 192-beam laser facility presently under construction at LLNL. When completed, NIF will be a 1.8-MJ, 500-TW ultraviolet laser system. Its missions are to obtain fusion ignition and to perform high energy density experiments in support of the US nuclear weapons stockpile. Four of the NIF beams have been commissioned to demonstrate laser performance and to commission the target area including target and beam alignment and laser timing. During this time, NIF demonstrated on a single-beam basis that it will meet its performance goals and demonstrated its precision and flexibility for pulse shaping, pointing, timing and beam conditioning. It also performed four important experiments for Inertial Confinement Fusion and High Energy Density Science. Presently, the project is installing production hardware to complete the project in 2009 with the goal to begin ignition experiments in 2010. An integrated plan has been developed including the NIF operations, user equipment such as diagnostics and cryogenic target capability, and experiments and calculations to meet this goal. This talk will provide NIF status, the plan to complete NIF, and the path to ignition.     

Calibration and evaluation of optical systems for full-field strain measurement

The design and testing of a reference material for the calibration of optical systems for strain measurement is described, together with the design and testing of a standardized test material that allows the evaluation and assessment of fitness for purpose of the most sophisticated optical system for strain measurement. A classification system for the steps in the measurement process is also proposed and allows the development of a unified approach to diagnostic testing of components or sub-systems in an optical system for strain measurement based on any optical technique. The results described arise from a European study known as SPOTS whose objectives were to begin to fill the gap caused by a lack of standards.     

Reductive dechlorination of hexachloroethane in the environment: mechanistic studies via computational electrochemistry.

Ab initio and density functional levels of electronic structure theory are applied to characterize alternative mechanisms for the reductive dechlorination of hexachloroethane (HCA) to perchloroethylene (PCE). Aqueous solvation effects are included using the SM5.42R continuum solvation model. After correction for a small systematic error in the electron affinity of the chlorine atom, theoretical predictions are accurate to within 23 mV for four aqueous reduction potentials relevant to HCA. A single pathway that proceeds via two successive single-electron transfer/barrierless chloride elimination steps, is predicted to be the dominant mechanism for reductive dechlorination. An alternative pathway predicted to be accessible involves trichloromethylchlorocarbene as a reactive intermediate. Bimolecular reactions of the carbene with other species at millimolar or higher concentrations are predicted to potentially be competitive with its unimolecular rearrangement to form PCE.     

Les Atomes: a landmark book in chemistry

There have been occasions when the publication of a particular book has had a singular impact on the conceptual world of the chemist. Sometimes the publication occurs near the beginning of a major change in discourse, and sometimes more near the end. Jean Perrin published Les Atomes in 1913 as the culmination of a century-long controversy over the size and physical reality of atoms and molecules. After its publication almost all chemists and physicists agreed that atoms and molecules of the size we currently understand to be appropriate are real physical objects. The story of the background, development, publication, content and response to Les Atomes forms the text of this paper. The content of Les Atomes is also the basis for extended reflection on the philosophical significance of the work of Jean Perrin.