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Content archived on 2024-04-16

MOLECULAR BEAM STUDIES OF ATOM AND FREE RADICAL REACTION DYNAMICS

Objective


Molecular beam studies of atom and free radical reaction dynamics have been carried out in the following areas:

Elastic and reactive scattering of fluorine and oxygen atom beams:
The reactive scattering of fluorine atoms with iodine containing molecules has been studied intensively. Reaction proceeds over a potential energy surface with a potential energy minimum which gives rise to a persistent collision complex. The lifetime of the complex and the dynamics of its dissociation to reaction products have been studied as a function of collision energy along the series of alkyl and allyl iodides and compared with the reactions of iodochlorine and diiodine molecules which show evidence for migratory dynamics. The long range form of the potential energy surfaces involved has been investigated by elastic scattering measurements of magnetically selected halogen atoms with inert gas atoms and hydrogen halide molecules. The reactions of oxygen atoms have also been studied using a microwave discharge source or using a radio frequency discharge.

Theoretical analysis of reactive scattering data;
2 complementary approaches have been taken to the interpretation of reactive scattering data. A new microcanonical transition state theory for the dissociation of persistent collision complexes has been developed together with trajectory studies of systems involving migratory dynamics. At the same time quantal descriptions of reactive scattering using hyperspherical coordinates have been developed.

Chemiionization processes:
2 complementary approaches to the study of chemiionization processes have also been taken with work involving studies of Penning, associative and rearrangement ionization arising from collisions of metastable electronically excited neon atoms with atoms and molecules as well as work on collisions of electronically excited alkali and alkaline earth atoms with halogen containing molecules.

Effect of molecular orientation on reactive scattering:
The rea ctions of metastable electronically excited calcium (1D) atoms with oriented methyl halide molecules have been studied using an electric hexapole focussing field, and the differences in reactivity at the methyl and halogen ends of the molecule have been detected using laser induced fluorescence.

Development of new experimental techniques:
Work on reaction dynamics has been extended to the study of surface reactions by observing the time dependant chemiluminescence of oxygen atom recombination with nitric oxide molecules using a newly constructed beam surface apparatus. The development of a supersonic free radical beam source using infrared laser pyrolysis is now well advanced, while new magnetically selected chlorine beam source has also been developed as has a pulsed beam source for low vapour pressure metal atom beams. A new design of microchannel plate detector has also been developed while new designs of electric hexapole field configurations have produced improved beams of oriented and state selected methyl halide molecules.
A collaboration is proposed between four European laboratories wich are engaged in the study of chemical reaction dynamics using molecular beam and laser techniques. A full understanding of the dynamics of non-alkali atom and free radical reactions requires very detailed investigations using a range of highly sophisticated experiments in order to gain an accurate description of the reaction potential energy surface. It is proposed to coordinate and develop the expertise which already exists in the participating laboratories, in undertaking measurements on reactions of fundemental importance using novel supersonic atom and free radical sources.

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Coordinator

UNIVERSITY OF MANCHESTER
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Oxford Road
M13 9PL MANCHESTER
United Kingdom

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Participants (4)

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