Journal
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
Volume 122, Issue 7, Pages -Publisher
WILEY
DOI: 10.1002/qua.26866
Keywords
dimerization of cyclooctatetraene; electron density; electron localization-delocalization matrices; potential energy surfaces; quantum theory of atoms in molecules
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Funding
- Nova Scotia Graduate Scholarship (NSGS)
- Scotia Scholars Award
- Alzheimer Society of Nova Scotia
- Natural Sciences and Engineering Research Council of Canada (NSERC)
- Canada Foundation for Innovation (CFI)
- Research Nova Scotia (RNS)
- Compute Canada
- Saint Mary's University
- Mount Saint Vincent University
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The study revisits the dimerization mechanism of cyclooctetraene (COT) using electron density and electron localization-delocalization matrices (LDMs). It is found that the rate-limiting step of the reaction is the penultimate transition state of a series of five transition states, and the dimer has a significant total dipole moment. Furthermore, the research shows that LDMs are excellent monitors of structural/electronic similarity.
The electron density and the electron localization-delocalization matrices (LDMs) are used to revisit the cyclooctetraene (COT) dimerization mechanism. The global minimum of a COT monomer (the tub geometry) exhibits a rare topological feature, giving rise, not to one, but to two ring critical points and a cage critical point necessary to satisfy the Poincare-Hopf relation. The energy profiles were used to identify the rate-limiting step of the reaction: the penultimate transition state of a series of five transition states in total. While the monomers themselves have zero dipolar polarization, the dimer has a nonnegligible total dipole moment reaching almost 1 debye with fluctuations in strength and orientation along the reaction path. The reaction can hence, possibly, be manipulated with intense laser fields. This classic reaction has been used to elucidate whether the electron LDMs reflect structural or energetic similarity. It is found that LDMs are excellent monitors of structural/electronic similarity between different species on the reaction coordinate. A reaction can be characterized by a three-dimensional hypermatrix whereby the matrix elements change as a function of the reaction coordinate, which can be represented as a parallelepiped of matrix elements. A study of the electron density of the system as the reaction progresses identifies and characterizes the bond paths that drive the reaction. It is hoped that this dynamic picture of the evolution of the electron density complements the usual arrow pushing reaction mechanisms used by organic chemists.
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