title: Stabilization of activated fragments by shell-wise construction of an embedding environment.
abstract: An activated fragment which is structurally unstable when considered isolated can be stabilized through binding to a suitable molecular environment; for instance, to a transition-metal fragment. The metal fragment may be designed in a shell-wise build-up of a surrounding molecular environment. However, adding more and more atoms in a consecutive fashion soon leads to a combinatorial explosion of structures, which is unfeasible to handle without automation. Here, we present a fully automated and parallelized framework that constructs such an embedding environment atom-wise. Molecular realizations of such an environment are constructed based on simple heuristic rules intended to screen a sufficiently large portion of the possible compound space and are then subsequently optimized by electronic structure methods. (Constrained-optimized) structures are then evaluated with respect to a scoring function, for which we choose here the concept of gradient-driven molecule construction. This concept searches for structure modifications that reduce the forces on all atoms. We develop and analyze our approach at the example of CO2activation by reproducing a known compound and mapping out possible alternative structures and their effect on the stabilization of a (bent) CO2ligand. For all generated structures, the nuclear gradient on the activated fragment and its coordination energy are evaluated to steer the design process. © 2017 Wiley Periodicals, Inc.
authors.affiliation: ETH Zürich, Laboratorium für Physikalische Chemie, Vladimir-Prelog-Weg 2, Zürich, CH-8093, Switzerland.
authors.forename: Florian
authors.initials: F
authors.lastname: Krausbeck
authors.affiliation: ETH Zürich, Laboratorium für Physikalische Chemie, Vladimir-Prelog-Weg 2, Zürich, CH-8093, Switzerland.
authors.forename: Jan-Grimo
authors.initials: JG
authors.lastname: Sobez
authors.affiliation: ETH Zürich, Laboratorium für Physikalische Chemie, Vladimir-Prelog-Weg 2, Zürich, CH-8093, Switzerland.
authors.forename: Markus
authors.identifier: 0000-0002-9508-1565
authors.initials: M
authors.lastname: Reiher
keywords: density functional theory; molecular design; transition metal chemistry