Issue 2, 2015

On the directionality and non-linearity of halogen and hydrogen bonds

Abstract

Benchmark quality structures and interaction energies have been produced using explicitly correlated coupled cluster methods for a systematic series of hydrogen and halogen bonded complexes: B⋯HCCH, B⋯HCl and B⋯ClF, with six different Lewis bases B. Excellent agreement with experimental structures is observed, verifying the method used to deduce the equilibrium deviation from collinearity of the intermolecular bond via rotational spectroscopy. This level of agreement also suggests that the chosen theoretical method can be employed when experimental equilibrium data are not available. The application of symmetry adapted perturbation theory reveals differences in the underlying mechanisms of interaction for hydrogen and halogen bonding, providing insights into the differences in non-linearity. In the halogen bonding case it is shown that the dispersion term is approximately equal to the overall interaction energy, highlighting the importance of choosing the correct theoretical method for this type of interaction.

Graphical abstract: On the directionality and non-linearity of halogen and hydrogen bonds

Supplementary files

Article information

Article type
Paper
Submitted
29 Jul 2014
Accepted
14 Aug 2014
First published
14 Aug 2014
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2015,17, 858-867

On the directionality and non-linearity of halogen and hydrogen bonds

J. Grant Hill and A. C. Legon, Phys. Chem. Chem. Phys., 2015, 17, 858 DOI: 10.1039/C4CP03376K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements