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How to Perform Distortion-Interaction Analysis

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posted on 2014-12-20, 21:52 authored by Robert PatonRobert Paton

This example, taken from Angew. Chem. Int. Ed. 2011, 50, 10366, ilustrates a distortion-interaction (alternatively activation strain) analysis for the Diels-Alder cycloaddition between cyclopentadiene and cyclobutenone.

The distortion-interaction model is ideally suited to a bimolecular reaction. In the example shown the reactants are optimized separately and the sum of their energies is defined as zero. The transition structure is obtained in the usual manner and from its energy the activation barrier may be calculated. The geometries of the two reactants are individually extracted from the TS geometry and the single point energies obtained. The difference between these energies and those of the optimized reactants is the distortion energy. The interaction energy, which is by definition always favourable (negative) is obtained from the difference between activation barrier and the summed distortion energies.

It goes without saying that the same level of theory/basis set is used throughout. Since the distorted geometries of the two reactants are not themselves stationary points on the potential energy surface, only the energy may be used for distortion interaction analysis (rather than, say, free energy).

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