Download or read book Time resolved Spectroscopic Studies of Chlorine and Bromine Atom Reactions in Solution written by and published by . This book was released on 2015 with total page 143 pages. Available in PDF, EPUB and Kindle. Book excerpt: Ultrafast time-resolved pump-probe spectroscopy monitors the dynamics of bimolecular reactions of Cl and Br atoms in solution with sub-picosecond time resolution. A photolysis pulse dissociates a given precursor to generate either Cl or Br atoms, and a UV/VIS or mid-IR probe pulse monitors the evolution of the atom or a reaction product. The hydrogen abstraction reactions of Cl and Br atoms with organic molecules are exoergic and endoergic, respectively. In the case of Br atom reaction, we introduce an additional near-IR pump pulse to promote this endoergic reaction using vibrational excitation. The reactions of Cl atoms with alkanes and alkenes exhibit rate constants that are diffusion-limited (or faster) and are ranked by the number of C=C bonds in the reactants. This suggests that an attractive intermolecular force between the Cl atom and the C=C bond influences the reaction rates. The reactions of Cl atoms with alkenes produce vibrationally excited HCl (v=1). The branching into HCl (v=1) shows a solvent viscosity dependence, owing to a dampening of the vibrational excitation. In contrast, the reaction rates are faster in a more-viscous solvent, implying a failure of simple diffusion theory in describing the reactions of Cl atoms with alkenes. In the reactions of Br atoms, we seek to realize the first vibrationally driven bimolecular reaction. Our most promising prospects are the reactions of Br atoms with CH3OH and DMSO. We observe a difference signal in the decay of the Br-solvent complex when the near-IR pump is resonant with the C-H or O-H overtone stretches of CH3OH and DMSO. This difference signal contains a negative offset at long times, which signifies a loss of the Br-solvent following vibrational excitation. This could be due to vibrational predisocciation of the complex, followed by either geminate recombination to re-form the solvent and the Br precursor or reaction of the Br atoms with vibrationally excited solvent molecules.

Download or read book Time resolved Spectroscopic Studies of Chlorine Radicals in Solution written by Leonid Sheps and published by . This book was released on 2005 with total page 244 pages. Available in PDF, EPUB and Kindle. Book excerpt:

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Download or read book Photochemistry written by Ian Dunkin and published by Royal Society of Chemistry. This book was released on 2007-10-31 with total page 288 pages. Available in PDF, EPUB and Kindle. Book excerpt: The breadth of scientific and technological interests in the general topic of photochemistry is truly enormous and includes, for example, such diverse areas as microelectronics, atmospheric chemistry, organic synthesis, non-conventional photoimaging, photosynthesis, solar energy conversion, polymer technologies, and spectroscopy. This Specialist Periodical Report on Photochemistry aims to provide an annual review of photo-induced processes that have relevance to the above wide-ranging academic and commercial disciplines, and interests in chemistry, physics, biology and technology. In order to provide easy access to this vast and varied literature, each volume of Photochemistry comprises sections concerned with photophysical processes in condensed phases, organic aspects which are sub-divided by chromophore type, polymer photochemistry, and photochemical aspects of solar energy conversion. Volume 34 covers literature published from July 2001 to June 2002. Specialist Periodical Reports provide systematic and detailed review coverage in major areas of chemical research. Compiled by teams of leading authorities in the relevant subject areas, the series creates a unique service for the active research chemist, with regular, in-depth accounts of progress in particular fields of chemistry. Subject coverage within different volumes of a given title is similar and publication is on an annual or biennial basis.