Edge versus interior in the chemical bonding and magnetism of zigzag edged triangular graphene molecules.
Ab initio density functional theory calculations show that the CC bond lengths fall into three distinct groups: core, apex, and edge, irrespective of whether the molecular center is a single atom or a C(6)-ring. The core, with a geometry that approximates infinite graphene, extends to the penultimate triangular row of carbon atoms, except in the vicinity of an apex. Impressed on the core bonds starting at the center is a small increasing length oscillation. The perimeter CC bonds joined at the apex are the shortest in the molecule. The edge carbon atoms are separated from interior atoms by the longest bonds in the molecule. The spin density localized primarily on edge (not apex) carbons with attached hydrogen (A-sublattice) is likely the highest attainable in any graphene molecule. The CC bonds in the high spin section of the edges are uniform in length and longer than perimeter CC bonds in the zigzag edged linear acenes, hexangulenes, annulenes, and benzene. This is attributed to the large number of edge localized nonbonding molecular orbitals (NBMOs) that sequestered pi-charge making it unavailable for bonding.
Philpott
Michael R
MR
Center for Computational Materials Science, Institute of Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, 980-8577 Sendai, Japan. philpott@imr.edu
Vukovic
Sinisa
S
Kawazoe
Yoshiyuki
Y
Lester
William A
WA