Issue 16, 2023

New insight into atomic-level interpretation of interactions in molecules and reacting systems

Abstract

We hereby introduce the atomic degree of interaction (DOI), a new concept rooted in the electron density-based independent gradient model (IGM). Capturing any manifestation of electron density sharing around an atom, including covalent and non-covalent situations, this index reflects the attachment strength of an atom to its molecular neighbourhood. It is shown to be very sensitive to the local chemical environment of the atom. No significant correlation could be found between the atomic DOI and various other atomic properties, making this index a specific source of information. However, examining the simple H2 + H reacting system, a strong connection has been established between this electron density-based index and the scalar reaction path curvature, the cornerstone of the benchmark unified reaction valley approach (URVA). We observe that reaction path curvature peaks appear when atoms experience an acceleration phase of electron density sharing during the reaction, detected by peaks of the DOI second derivative either in the forward or reverse direction. This new IGM-DOI tool is only in its early stages, but it opens the way to an atomic-level interpretation of reaction phases. More generally, the IGM-DOI tool may also serve as an atomic probe of electronic structure changes of a molecule under the influence of physicochemical perturbations.

Graphical abstract: New insight into atomic-level interpretation of interactions in molecules and reacting systems

Supplementary files

Article information

Article type
Paper
Submitted
22 Jun 2022
Accepted
27 Mar 2023
First published
31 Mar 2023

Phys. Chem. Chem. Phys., 2023,25, 11398-11409

New insight into atomic-level interpretation of interactions in molecules and reacting systems

C. Lefebvre, H. Khartabil and E. Hénon, Phys. Chem. Chem. Phys., 2023, 25, 11398 DOI: 10.1039/D2CP02839E

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements