More Stable Template Localization for an Incremental Focal-Point ApproachImplementation and Application to the Intramolecular Decomposition of Tris-perfluoro-tert-butoxyalane

• Published in: Journal of chemical theory and computation Vol. 14; no. 2; pp. 557 - 571
• Main Authors: Fiedler, Benjamin, Himmel, Daniel, Krossing, Ingo, Friedrich, Joachim
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 13.02.2018
• Subjects: Decomposition; Functionals; Localization
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.7b00707

We present a new implementation of the template localization for the fully automated and parallizable incremental method, which excludes failures of this important step within the domain-specific basis set approach and thus ensures a higher reliability of the scheme, preserving its very high accuracy. Furthermore, we combine our method with an efficient focal-point ansatz to reach the complete basis set limit and carefully assess this approach for the first time with regard to reaction energies. For a test set of 51 reactions the incremental focal-point method with a basis set of moderate size provides a very high accuracy with respect to the complete basis set limit. That way, we are finally able to apply the scheme as a benchmark method (e.g., for density functionals) in the context of a relevant chemical topic, the intramolecular decomposition of tris-perfluoro-tert-butoxyalane (43 heavy atoms, 352 electrons).