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Photophysics and Spectroscopy of Hydrides, Ions and Organic Radicals


PHOSPHOR: Photo physics and Spectroscopy of Hydrides, ions and Organic Radicals Processes that convert electronic excitation into nuclear kinetic energy largely determine the photo physics of platonic molecules in excited electronic states. Such processes are ubiquitous - in scientific areas ranging from atmospheric chemistry to photobiology, and from molecular electronics to Nan science. In the language of chemical physics, such processes represent a breakdown of the so-called Born-Oppenheimer approximation that underpins almost all of our thinking in the areas of molecular structure, spectroscopy and dynamics. Central to such thinking is the concept of the potential energy surface, on which reactants evolve to products. Recently evidence has been accumulating from both experimental and theoretical studies that the atoms and molecules can switch between electronic states during bond breakage and formation processes. Such processes are described as non-adiabatic and are driven by couplings between the ground and higher lying adiabatic Pass that are neglected within the Born-Oppenheimer approximation. This proposal seeks to apply cutting-edge laser based experimental techniques, particularly velocity map ion imaging methods and H (Ryder) photo fragment transactional spectroscopy, to investigate details of the primary photo physics and photo fragmentation physics of a carefully chosen range of molecules, organic free radical species, and state selected molecular ions. Each family of experiments involves innovative state-of-the- art experimentation, and will be backed up by detailed theoretical interpretation. In this way, we expect to accumulate detailed insights into the role of non-adiabatic effects in the fragmentation of different classes of molecular system (both closed-shell, and open-shell), thereby building towards a much fuller understanding of non-adiabatic couplings and their influence on molecular reactivity.

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