A Bond Bundle Case Study of Diels-Alder Catalysis Using Oriented Electric Fields

06 January 2022, Version 2
This content is a preprint and has not undergone peer review at the time of posting.


Bond bundles are chemical bonding regions, analogous to Bader atoms, uniquely defined according to the topology of the gradient bundle condensed charge density, itself obtained by a process of infinitesimal partitioning of the three-dimensional charge density into differential zero-flux surface bounded regions. Here we use bond bundle analysis to investigate the response of the charge density to an oriented electric field in general, and the catalytic effect of such a field on Diels-Alder reactions in particular, which in this case is found to catalyze by allowing the transition state valance bond bundle configuration to be achieved earlier along the reaction pathway. Using precise numerical values, we arrive at the conclusion that chemical reactions and electric field catalysis can be understood in terms of intra-atomic charge density redistribution, i.e., that charge shifts within more so than between atoms account for the making and breaking of bonds.


bond bundles
gradient bundle analysis
gradient bundle
electric field catalysis
electron density analysis

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