Experimental and theoretical studies of the hydrogen exchange reaction

Citation

Giorgi, Maria Rebecca (1992) Experimental and theoretical studies of the hydrogen exchange reaction. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/m4a8-mm29. https://resolver.caltech.edu/CaltechTHESIS:09082011-073645691

Abstract

This thesis consists of experimental and theoretical efforts to better understand the hydrogen exchange reaction. Colinear quantum mechanical calculations were conducted on the isotopic H + H_2 reaction, using the method of hyperspherical coordinates. Reaction probabilities and rate constants have been obtained for thirteen isotopic hydrogenic systems, and the results compared to those of conventional transition state theory and transition state theory with quantum corrections. The validity of the conservation of vibrational energy (CVE) and the vibrationally adiabatic (VA) approximations were tested. It was found that the VA approximation gives fairly accurate rate constants, although it is inadequate at predicting low temperature isotope effects. On the other hand, conventional transition state theory predicts isotope effects accurately, except in the cases where tunnelling is a major effect, such as the H_3 system.

The second part of the thesis illustrates the technique of vacuum ultraviolet laser induced fluorescence for the state-specific detection of molecular hydrogen. Preliminary investigations of the potential application of the LIF technique to the detection of products of the hydrogen exchange reaction are described.

Thesis Files