RT Journal Article
T1 Electrostatic penetration effects stand at the heart of aromatic π interactions
A1 Cabaleiro Lago, Enrique Manuel
A1 Rodríguez Otero, Jesús
A1 Vázquez Rodríguez, Saulo Ángel
K1 Dímeros
K1 Benceno
K1 SAPT
AB The nature of the interaction in benzene-containing dimers has been analysed by means of Symmetry Adapted Perturbation Theory (SAPT). The total interaction energy and the preference for the dimers to adopt slipped structures are, apparently, consequence of the balance between repulsion and dispersion. However, our results indicate that this only holds when trends are analysed using fixed intermolecular distances. Employingthe most favourable separations between rings it turns out that the changes on the total interaction energy are mostly controlled by electrostatics, while repulsion and dispersion cancel each other to a great extent. Most of the electrostatic contribution is accounted for by electrostatic penetration, so a description based on multipoles should not be employed to rationalise the interaction in benzene-containing dimers. The changes on the interaction energy in benzene-containing dimers are steered by electrostatic penetration which, though often overlooked, plays an essential role for the description of aromatic π interactions
PB Royal Society of Chemistry
SN 1463-9076
YR 2022
FD 2022
LK https://hdl.handle.net/10347/38773
UL https://hdl.handle.net/10347/38773
LA eng
NO Cabaleiro-Lago, E. M., Rodríguez-Otero, J., Vázquez, S. A. (2022). Electrostatic penetration effects stand at the heart of aromatic π interactions. "Physical Chemistry Chemical Physics", vol. 24(15), 8979-8991
NO The authors thank the financial support from the Consellería de Cultura, Educación e Ordenación Universitaria e da Consellería de Economía, Emprego e Industria (Axuda para Consolidación e Estruturación de unidades de investigación competitivas do Sistema Universitario de Galicia, Xunta de Galicia ED431C 2021/40). The authors also want to express their gratitude to the CESGA (Centro de Supercomputación de Galicia) for the use of their computers
DS Minerva
RD 28 abr 2026