Revisiting van der Waals Radii: From Comprehensive Structural Analysis to Knowledge-Based Classification of...

Area of Science:

• Supramolecular Chemistry
• Computational Chemistry
• Biophysics

Background:

• Weak noncovalent interactions govern the structure and properties of essential biological and material systems, including nucleic acids, enzymes, and pharmaceutical crystals.
• Analyzing the precise role and significance of these interactions is complex and often necessitates simplified model studies.

Purpose of the Study:

• To introduce an efficient and universal computational approach for analyzing noncovalent interactions.
• To enable the accurate determination of van der Waals radii within complex molecular systems.
• To provide a quantitative method for assessing the specificity, anisotropy, and steric effects of intermolecular interactions.

Main Methods:

• Development and application of the line-of-sight (LoS) concept for analyzing interatomic contacts.
• Utilizing the LoS method to identify and classify direct interatomic contacts in various molecular systems.
• Applying the LoS approach to determine van der Waals radii and quantify interaction characteristics.

Main Results:

• The line-of-sight (LoS) concept provides an unambiguous method for identifying and classifying direct interatomic contacts.
• The LoS approach establishes an improved theoretical foundation for defining molecular sizes.
• Quantitative analysis of interaction specificity, anisotropy, and steric effects is enabled by this new methodology.

Conclusions:

• The LoS method offers an efficient and universal tool for the analysis of noncovalent interactions and van der Waals radii.
• This approach enhances the understanding of molecular structure and properties by providing a robust framework for analyzing intermolecular forces.
• The LoS concept facilitates more accurate predictions and designs in fields reliant on supramolecular assembly and interactions.