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An atomic surface site interaction point description of non-covalent interactions.

Accepted version
Peer-reviewed

Change log

Authors

Storer, Maria Chiara  ORCID logo  https://orcid.org/0000-0002-3668-1333
Reynolds, Derek P 
Hunter, Christopher A  ORCID logo  https://orcid.org/0000-0002-5182-1859

Abstract

Molecular electrostatic potential surfaces (MEPS) calculated using density functional theory have been used to develop a simplified description of the non-covalent interaction properties of organic molecules. The Atomic Interaction Point (AIP) model introduced here represents an evolution of the Surface Site Interaction Point (SSIP) model described previously, in which a molecule is represented by a discrete set of interaction points that define sites of interaction with other molecules. The interaction sites are described by interaction parameters that are equivalent to the experimentally determined H-bond donor and acceptor parameters α and β. By using high electron density MEPS that lie inside the van der Waals surface, it is possible to obtain accurate interaction parameters and locations for polar sites (s-holes, H-bond donors and acceptors), which are identified as local maxima and minima on the MEPS. For non-polar sites that represent π-systems and halogens, an approach based on molecular orbitals was used to assign the locations of the AIPs, and the interaction parameters were obtained using a lower electron density MEPS that lies close to the van der Waals surface. The AIP descriptions can be implemented directly in the Surface Site Interaction Point Model for Liquids at Equilibrium (SSIMPLE) to calculate solvation free energies, and the free energy of transfer of 1504 compounds from n-hexadecane to water was predicted with a root mean square error of 5 kJ mol-1. AIPs also provide a useful tool for mapping non-covalent interactions in intermolecular complexes, and examples are provided showing how X-ray crystal structures can be converted into AIP interaction maps that allow quantification of the free energy contributions of both polar and non-polar interactions to the stabilities of complexes in solution.

Description

Keywords

34 Chemical Sciences, 3406 Physical Chemistry, 3407 Theoretical and Computational Chemistry

Journal Title

Chem Sci

Conference Name

Journal ISSN

2041-6520
2041-6539

Volume Title

Publisher

The Royal Society of Chemistry
Sponsorship
Engineering and Physical Sciences Research Council (EP/S024220/1)
Engineering and Physical Sciences Research Council (EP/S024220/1) and the Herchel Smith Fund