Cabaleiro Lago, Enrique ManuelRodríguez Otero, Jesús2019-10-262019-10-262018-08-17Cabaleiro-Lago, E., & Rodríguez-Otero, J. (2018). On the Nature of σ–σ, σ–π, and π–π Stacking in Extended Systems. ACS Omega, 3(8), 9348-9359. doi: 10.1021/acsomega.8b013392470-1343http://hdl.handle.net/10347/19958Stacking interactions have been evaluated, employing computational methods, in dimers formed by analogous aliphatic and aromatic species of increasing size. Changes in stability as the systems become larger are mostly controlled by the balance of increasing repulsion and dispersion contributions, while electrostatics plays a secondary but relevant role. The interaction energy increases as the size of the system grows, but it does much faster in π–π dimers than in σ–π complexes and more remarkably than in σ–σ dimers. The main factor behind the larger stability of aromatic dimers compared to complexes containing aliphatic molecules is related to changes in the properties of the aromatic systems due to electron delocalization leading to larger dispersion contributions. Besides, an extra stabilization in π–π complexes is due to the softening of the repulsive wall in aromatic species that allows the molecules to come closerengCopyright © 2018 American Chemical Society. This is an open access article published under an ACS AuthorChoice License, which permitscopying and redistribution of the article or any adaptations for non-commercial purposes (https://pubs.acs.org/page/policy/authorchoice_termsofuse.html)Aromatic compoundsColloidsHydrocarbonsInteraction energiesjournal article10.1021/acsomega.8b01339open access