Structure and Electron Delocalization in Al4(2-) and Al4(4.)

Rafael Islas; Thomas Heine; Gabriel Merino

doi:10.1021/ct700009k

Structure and Electron Delocalization in Al4(2-) and Al4(4.)

J Chem Theory Comput. 2007 May;3(3):775-81. doi: 10.1021/ct700009k.

Authors

Rafael Islas¹, Thomas Heine¹, Gabriel Merino¹

Affiliation

¹ Facultad de Química, Universidad de Guanajuato, Noria Alta s/n, Guanajuato, Gto, 36050, México, and Institut für Physikalische Chemie und Elektrochemie, TU Dresden, D-01062 Dresden, Germany.

PMID: 26627395
DOI: 10.1021/ct700009k

Abstract

Structure, dynamics, and electron delocalization of Al4(2-) and Al4(4-) based clusters are investigated. Gradient-corrected Density-Functional Born-Oppenheimer Molecular Dynamics simulations indicate that Al4(2-) based clusters have a rigid planar Al framework, while the Al4(4-) based moieties show large distortions from planarity. The induced magnetic field analysis of these species indicates that both systems have diatropic σ-systems, while the π-system is diatropic for Al4(2-) and paratropic for Al4(4-). The total magnetic response is diatropic for Al4(2-), while Al4(4-) is "bitropic": it has typical antiaromatic long-range cones, while the magnetic field in the Al4(4-) ring plane is similar to that of aromatic annulenes.