Quantum effects in unimolecular reaction dynamics

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This work is primarily concerned with the development of models for the quantum dynamics of unimolecular isomerization and photodissociation reactions. We apply the rigorous quantum methodology of a Discrete Variable Representation (DVR) with Absorbing Boundary Conditions (ABC) to these models in an attempt to explain some very surprising results from a series of experiments on vibrationally excited ketene. Within the framework of these models, we are able to identify the experimental signatures of tunneling and dynamical resonances in the energy dependence of the rate of ketene isomerization. Additionally, we investigate the step-like features in the energy dependence of the rate ... continued below

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130 p.

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Gezelter, J.D. December 1, 1995.

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Description

This work is primarily concerned with the development of models for the quantum dynamics of unimolecular isomerization and photodissociation reactions. We apply the rigorous quantum methodology of a Discrete Variable Representation (DVR) with Absorbing Boundary Conditions (ABC) to these models in an attempt to explain some very surprising results from a series of experiments on vibrationally excited ketene. Within the framework of these models, we are able to identify the experimental signatures of tunneling and dynamical resonances in the energy dependence of the rate of ketene isomerization. Additionally, we investigate the step-like features in the energy dependence of the rate of dissociation of triplet ketene to form {sup 3}B{sub 1} CH{sub 2} + {sup 1}{sigma}{sup +} CO that have been observed experimentally. These calculations provide a link between ab initio calculations of the potential energy surfaces and the experimentally observed dynamics on these surfaces. Additionally, we develop an approximate model for the partitioning of energy in the products of photodissociation reactions of large molecules with appreciable barriers to recombination. In simple bond cleavage reactions like CH{sub 3}COCl {yields} CH{sub 3}CO + Cl, the model does considerably better than other impulsive and statistical models in predicting the energy distribution in the products. We also investigate ways of correcting classical mechanics to include the important quantum mechanical aspects of zero-point energy. The method we investigate is found to introduce a number of undesirable dynamical artifacts including a reduction in the above-threshold rates for simple reactions, and a strong mixing of the chaotic and regular energy domains for some model problems. We conclude by discussing some of the directions for future research in the field of theoretical chemical dynamics.

Physical Description

130 p.

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OSTI as DE96007751

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  • Other Information: TH: Thesis (Ph.D.)

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  • Other: DE96007751
  • Report No.: LBL--38165
  • Grant Number: AC03-76SF00098
  • Office of Scientific & Technical Information Report Number: 211627
  • Archival Resource Key: ark:/67531/metadc671766

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Office of Scientific & Technical Information Technical Reports

Reports, articles and other documents harvested from the Office of Scientific and Technical Information.

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  • December 1, 1995

Added to The UNT Digital Library

  • June 29, 2015, 9:42 p.m.

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  • Aug. 23, 2016, 3:56 p.m.

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Gezelter, J.D. Quantum effects in unimolecular reaction dynamics, thesis or dissertation, December 1, 1995; California. (digital.library.unt.edu/ark:/67531/metadc671766/: accessed November 19, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.