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Theoretical studies of state resolved molecular collision dynamics

Thesis/Dissertation ·
OSTI ID:6750688

This dissertation is a collection of three projects in theoretical chemical dynamics. The first is a study of the state-to-state dynamics of the H + H/sub 2/O ..-->.. OH + H/sub 2/ reaction. Quasiclassical trajectory cross sections and rate constants are presented as well as a detailed study of reagent normal-mode and local-mode excitation effects and product-state energy partitioning. The ground-state thermal rate constants are compared with experimental measurements and are found to agree within their respective uncertainties. The second project is a study of the NO vibration/rotation distributions produced in nonreactive H + NO collisions. Details of the collisions are analyzed and it is found that complex formation plays a very important role in the H + NO collision dynamics. The last project is a study of the H + H/sub 2/ reactions and its isotopic counterparts D + H/sub 2/ and H + D/sub 2/. For all three reactions, integral cross sections and rate constants are reported. The reaction dynamics is studied using quantum reactive scattering methods based on the coupled-states (CS) approximation and the Liu-Siegbahn-Truhlar-Horowitz (LSTH) potential surface. These cross sections and rate constants compare very well with results from other calculational methods and experimental measurements. In connection with the H + H/sub 2/ reaction, the question is also addressed of resonances in which the metastable H/sub 3/ species is formed during the course of the reaction.

Research Organization:
Northwestern Univ., Evanston, IL (USA)
OSTI ID:
6750688
Country of Publication:
United States
Language:
English