Structure, Properties, and Applications of Silica Nanoparticles: Recent Theoretical Modeling Advances, Challenges, and Future Directions

Abstract Silica nanoparticles (SNPs), one of the most widely researched materials in modern science, are now commonly exploited in surface coatings, biomedicine, catalysis, and engineering of novel self‐assembling materials. Theoretical approaches are invaluable to enhancing fundamental understanding of SNP properties and behavior. Tremendous research attention is dedicated to modeling silica structure, the silica‐water interface, and functionalization of silica surfaces for tailored applications. In this review, the range of theoretical methodologies are discussed that have been employed to model bare silica and functionalized silica. The evolution of silica modeling approaches is detailed, including classical, quantum mechanical, and hybrid methods and highlight in particular the last decade of theoretical simulation advances. It is started with discussing investigations of bare silica systems, focusing on the fundamental interactions at the silica‐water interface, following with a comprehensively review of the modeling studies that examine the interaction of silica with functional ligands, peptides, ions, surfactants, polymers, and carbonaceous species. The review is concluded with the perspective on existing challenges in the field and promising future directions that will further enhance the utility and importance of the theoretical approaches in guiding the rational design of SNPs for applications in engineering and biomedicine.