Applications of thermodynamic integration: studying chemical reactions
Date
2008
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Abstract
The present work examines the theoretical foundation of thermodynamic integration (TI) and applies it to study chemical reactions.
First, a hypotetical chemical reaction is examined to demonstrate that the average force along a constraint in a molecular dynamics simulation is the negative of the derivative of the free energy.
Next, the benzyl-isocyanide isomerization and the butene-plus-singlet-oxygen reaction were investigated using TI. For the benzyl-isocyanide isomerization, activation parameters calculated using TI compared well to experiment. Also, thermodynamic properties specific to the phenyl rotation were calculated. For the butene-plus-singletoxygen reaction, one methyl group is deuterated. With the linear constraint active in the molecular dynamics, free energy along the path leading to deuterium abstraction was calculated. There exists a barrier for the free energy profile while no such barrier exists for the potential energy profile.
Two other reactions are proposed for future research: hydroboration rearrangement and the Staudinger reaction.
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Bibliography: p. 75-79
Some pages are in colour.
Some pages are in colour.
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Citation
Jechow, J. (2008). Applications of thermodynamic integration: studying chemical reactions (Master's thesis, University of Calgary, Calgary, Canada). Retrieved from https://prism.ucalgary.ca. doi:10.11575/PRISM/1998