Evaluating the predictive character of the method of constrained geometries simulate external force with density functional theory

Wick C, Topraksal E, Smith DM, Smith AS (2022)

Publication Type: Journal article

Publication year: 2022

Journal

Forces in Mechanics Elsevier

Book Volume: 9

Article Number: 100143

DOI: 10.1016/j.finmec.2022.100143

Abstract

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 earlier 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.

Authors with CRIS profile

Christian Wick Physics Underlying Life Science Ece Topraksal Lehrstuhl für Theoretische Physik Ana-Suncana Smith Physics Underlying Life Science

Additional Organisation(s)

Graduiertenkolleg 2423 Skalenübergreifende Bruchvorgänge: Integration von Mechanik, Materialwissenschaften, Mathematik, Chemie und Physik

Involved external institutions

Rudjer Boskovic Institute (RBI) / Institut Ruđer Bošković (IRB) HR Croatia (HR)

How to cite

APA:

Wick, C., Topraksal, E., Smith, D.M., & Smith, A.-S. (2022). Evaluating the predictive character of the method of constrained geometries simulate external force with density functional theory. Forces in Mechanics, 9. https://dx.doi.org/10.1016/j.finmec.2022.100143

MLA:

Wick, Christian, et al. "Evaluating the predictive character of the method of constrained geometries simulate external force with density functional theory." Forces in Mechanics 9 (2022).

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