The Molecular Surface Property Approach: A Guide to Chemical Interactions in Chemistry, Medicine, and Material Science

Abstract

The current status of the molecular surface property approach (MSPA) and its application for analysis and prediction of intermolecular interactions, including chemical reactivity, are reviewed. The MSPA allows for identification and characterization of all potential interaction sites of a molecule or nanoparticle by the computation of one or more molecular properties on an electronic isodensity surface. A wide range of interactions can be analyzed by three properties, which are well-defined within Kohn-Sham density functional theory. These are the electrostatic potential, the average local ionization energy, and the local electron attachment energy. The latter two do not only reflect the electrostatic contribution to a chemical interaction, but also the contributions from polarization and charge transfer. It is demonstrated that the MSPA has a high predictive capacity for non-covalent interactions, for example, hydrogen and halogen bonding, as well as organic substitution and addition reactions. The latter results open up applications within drug design and medicinal chemistry. The application of MSPA has recently been extended to nanoparticles and extended surfaces of metals and metal oxides. In particular, nanostructural effects on the catalytic properties of noble metals are rationalized. The potential for using MSPA in rational design of heterogeneous catalysts is discussed. Tore Brinck is professor of physical chemistry at KTH Royal Institute of Technology in Stockholm, Sweden. He received his M.Sc. in chemical engineering from KTH in 1990, and his Ph.D. from the University of New Orleans in 1993 with Prof. Peter Politzer as Ph.D. advisor. His research involves the development of electronic descriptors for the analysis of chemical reactivity, as well as the application of electronic structure methods to the analysis of chemical reactions in condensed phases. He also uses computational chemistry to study enzyme design, heterogeneous catalysis, and energetic materials. Joakim Halldin Stenlid is a postdoctoral fellow in the group of Prof. Lars GM Pettersson at Stockholm University where he is carrying out computational studies in electrochemistry and heterogeneous catalysis. He obtained his Ph.D. in physical chemistry from KTH

Not Only Hydrogen Bonds: Other Noncovalent Interactions

“…. ), proposed a division of σ-holes, depending on the molecular electrostatic potential, into σ s , σ p , and σ d -holes [61,62]. The higher the oxidation degree (for instance, Au(III) vs.…”

Machine learning meets mechanistic modelling for accurate prediction of experimental activation energies

“…For the E s,min descriptor this effect has been shown to be substantial. 34,55 Thirdly, the solvent correction can likely be learnt implicitly also from the other features for problematic nucleophiles such as those with anionic oxygen. This aspect is also connected to the fourth factor, that solvent variation is low for the anionic nucleophiles, where for example reactions with oxygen nucleophiles are only carried out in water or methanol ( Figure S25).…”

Halogen bond in separation science: A critical analysis across experimental and theoretical results

“…In particular, -hole being a region of electronic charge density depletion, calculated V S (r) has been widely used as an indicator of the anisotropy of the molecular charge distribution. In this regard, the evaluation of the V S,max on the halogen surfaces allows for a quantitative estimation of the -hole depth [42] which, in turn, determines the capability of a halogen as XB donor.…”