Predicting mechanochemical reactivity with the method of Constrained Geometries Simulate External Force

## Abstract from [1]: Mechanochemistry is a fast-developing field of interdisciplinary research with a growing number of applications. Therefore, many theoretical methods have been developed to quickly predict the outcome of mechanically induced reactions. Constrained geometries simulate External Force (CoGEF) is one of the pioneering methods in this field. It is easily implemented and can be conducted with most DFT codes. However, recently, we observed totally different predictions for model systems of epoxy resins in different conformations and with different density functionals. To better understand the conformational and functional dependence in typical CoGEF calculations we present a systematic evaluation of the CoGEF method for different model systems covering homolytic and heterolytic bond cleavage reactions, electrocyclic ring opening reactions and scission of non-covalent interactions in hydrogen-bond complexes. From our calculations we observe that many mechanochemical descriptors strongly depend on the functional used, however, a systematic trend exists for the relative maximum Force. In general, we observe that the CoGEF procedure is forcing the system to high energetic regions on the molecular potential energy profiles, which can lead to unexpected and uncorrelated predictions of mechanochemical reactions. This is questioning the true predictive character of the method. ## Contact Christian R. Wick Friedrich-Alexander-University Erlangen-Nürnberg (FAU), Faculty of Science, Department of Physics, PULS Group, Interdisciplinary Center for Nanostructured Films (IZNF), Cauerstrasse 3, 91058, Germany ## License Creative Commons Attribution 4.0 International ## Context Dataset to paper: [1] C. R. Wick, E. Topraksal, D. M. Smith, A.-S. Smith, "Predicting mechanochemical reactivity with the method of Constrained Geometries Simulate External Force", submitted to Forces in Mechanics All COGEF trajectories. ## Folder structure compound_X : data set for compound number X (numbering corresponds to the numbering scheme in [1]) the xyz trajectories follow the following naming convention: "DFT_method"_"unrestricted/restricted".xyz ## Funding This research was funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) - 377472739/GRK 2423/1-2019 FRASCAL. <br>