Ziegler, TomJechow, Jason2017-12-182017-12-182008Jechow, 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/1998http://hdl.handle.net/1880/102999Bibliography: p. 75-79Some pages are in colour.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.viii, 79 leaves : ill. ; 30 cm.engUniversity of Calgary graduate students retain copyright ownership and moral rights for their thesis. You may use this material in any way that is permitted by the Copyright Act or through licensing that has been assigned to the document. For uses that are not allowable under copyright legislation or licensing, you are required to seek permission.master thesis10.11575/PRISM/1998