Browsing by Author "Jechow, Jason"
Now showing 1 - 1 of 1
Results Per Page
Sort Options
Item Open Access Applications of thermodynamic integration: studying chemical reactions(2008) Jechow, Jason; Ziegler, TomThe 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.