Issue 2, 2018

Characterizing the interplay of Pauli repulsion, electrostatics, dispersion and charge transfer in halogen bonding with energy decomposition analysis

Abstract

The halogen bond is a class of non-covalent interaction that has attracted considerable attention recently. A widespread theory for describing them is the σ-hole concept, which predicts that the strength of the interaction is proportional to the size of the σ-hole, a region of positive electrostatic potential opposite a σ bond. Previous work shows that in the case of CX3I, with X equal to F, Cl, Br, and I, the σ-hole trend is exactly opposite to the trend in binding energy with common electron pair donors. Using energy decomposition analysis (EDA) applied to a potential energy scan as well as the recent adiabatic EDA technique, we show that the observed trend is a result of charge transfer. Therefore a picture of the halogen bond that excludes charge transfer cannot be complete, and permanent and induced electrostatics do not always provide the dominant stabilizing contributions to halogen bonds. Overall, three universally attractive factors, polarization, dispersion and charge transfer, together with permanent electrostatics, which is usually attractive, drive halogen bonding, against Pauli repulsion.

Graphical abstract: Characterizing the interplay of Pauli repulsion, electrostatics, dispersion and charge transfer in halogen bonding with energy decomposition analysis

Article information

Article type
Paper
Submitted
11 Oct 2017
Accepted
10 Nov 2017
First published
10 Nov 2017

Phys. Chem. Chem. Phys., 2018,20, 905-915

Characterizing the interplay of Pauli repulsion, electrostatics, dispersion and charge transfer in halogen bonding with energy decomposition analysis

J. Thirman, E. Engelage, S. M. Huber and M. Head-Gordon, Phys. Chem. Chem. Phys., 2018, 20, 905 DOI: 10.1039/C7CP06959F

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